REVIEW www.advmat.de Rational Design of Stimuli-Responsive Inorganic 2D Materials via Molecular Engineering: Toward Molecule-Programmable Nanoelectronics Jose Muñoz Moore’s law, postulating that computing The ability of electronic devices to act as switches makes digital information power doubles ≈18 months, and there- processing possible. Succeeding graphene, emerging inorganic 2D materials fore the dimensions must be reduced by (i2DMs) have been identified as alternative 2D materials to harbor a variety of 50% in this above-mentioned duration of active molecular components to move the current silicon-based time.[1] Despite their efficiency, the diffi- culty of downsizing owing to their costly semiconductor technology forward to a post-Moore era focused on top-down photolithography-based manu- molecule-based information processing components. In this regard, i2DMs facturing principle is approaching their benefits are not only for their prominent physiochemical properties (e.g., the physical limit due to Moore’s law. Con- existence of bandgap), but also for their high surface-to-volume ratio rich in sequently, a new technological post-Moore reactive sites. Nonetheless, since this field is still in an early stage, having era has started with the objective of pro- viding value-added programmable nano- knowledge of both i) the different strategies for molecularly functionalizing electronics by implanting new function- the current library of i2DMs, and ii) the different types of active molecular alities that do not necessary scale ac- components is a sine qua non condition for a rational design of cording to Moore’s law.[2–8] In this re- stimuli-responsive i2DMs capable of performing logical operations at the gard, 2D materials can provide a per- molecular level. Consequently, this Review provides a comprehensive tutorial fect solution owing to their atomically for covalently anchoring ad hoc molecular components—as active units layered scaling structure and bottom-up functionalization principle, viewing them triggered by different external inputs—onto pivotal i2DMs to assess their role as perfect building blocks to program in the expanding field of molecule-programmable nanoelectronics for the conductive behavior of electronic de- electrically monitoring bistable molecular switches. Limitations, challenges, vices at extreme nanoscale dimensions.[9,10] and future perspectives of this emerging field which crosses materials 2D materials, as atomically thin layered chemistry with computation are critically discussed. materials, have been placed in a pioneering position to lead the next “nanoelectronics revolution,” which pursues to complement or even replace Si-based semiconductors in post-Moore electronics.[5,11–15] Their ultimate thinness in com- 1. Introduction bination with their high surface area plenty of reactive sites To date, the fabrication of electronics has been mainly mo- represents an excellent atomic structure not only to move elec- nopolized by the conventional Si-based semiconductor proces- trons, but also to harbor active molecules.[16–18] Indeed, this sors. The road-map in Si-based electronic devices development represents pivotal characteristics to reach novel nanoarchitec- has been well defined by a technoeconomic model known as tures for the development of new forms of computation with ability to process logical binary information at the molecular level. Considering the outstanding results in the field obtained J. Muñoz Departament de Química by mainstream graphene (the best known 2D material) and Universitat Autònoma de Barcelona taking into account its absence of energy gap—fact that can Cerdanyola del Vallès, Barcelona 08193, Spain hinder the proper implementation of graphene toward logic E-mail: josemaria.munoz@uab.cat applications—,[19–23] the Materials Chemistry community has The ORCID identification number(s) for the author(s) of this article moved to explore alternative 2D materials exhibiting comple- can be found under https://doi.org/10.1002/adma.202305546 mentary features, viz., inorganic 2D materials (i2DMs).[24,25] © 2023 The Authors. Advanced Materials published by Wiley-VCH Amongst the wide family of i2DMs—including graphene- GmbH. This is an open access article under the terms of the Creative analogous single-element derivatives (known as Xenes),[26–29] Commons Attribution-NonCommercial-NoDerivs License, which permits 2D transition-metal chalcogenides (TMCs),[30–33] 2D transition- use and distribution in any medium, provided the original work is metal carbides/nitrides (MXenes),[34–37] and 2D transition-metal properly cited, the use is non-commercial and no modifications or adaptations are made. oxides and hydroxides (TMOs and TMHs, respectively)—,[38–41] semiconductor i2DMs have gained a lot of interest since most DOI: 10.1002/adma.202305546 Adv. Mater. 2023, 2305546 2305546 (1 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de of their inherent characteristics (e.g., bandgap) can be entirely carbon nanotubes[91] (1D), the field of 2D materials had a turn- tuned/modulated by tailoring the nature of the surface sub- ing point in 2004 after the isolation of graphene from graphite, stituent via anchoring active molecular components.[42–45] which was first reported by Novoselov et al.[23] 2D materials ben- In this line, molecular engineering has been positioned as a efit from their thin layered skeleton that provides them with out- key eco-friendly technology for the development of functional standing physicochemical properties different from those of their materials,[46–52] making it possible the confinement of active bulk counterparts. For example, graphene, the most studied 2D molecular components onto passive semiconductor materials material, exhibits excellent electrical, thermal, optical, and me- by employing sustainable bottom-up synthetic methods. Thus, chanical features, amongst other, making it attractive for being molecular engineering allows for the design of molecule-based used in a vast number of applications.[92–101] Nonetheless, some functional materials exhibiting responsiveness to external stim- applications of graphene in the nanoelectronics field are limited uli, fact that can promote bistable molecular switches through due to the zero bandgap. Indeed, the bandgap is one of the most the translation of a nanoscale signal into a readable macroscopic important parameters in electronic devices, since its presence is effect.[53,54] Although extremely motivating from a scientific point imperative to promote interband tunneling for switchability.[22] of view, a key challenge in the field relies on retaining the bista- Consequently, the field of nanoelectronics demands to explore bility of the active molecules exposed on the material’s surface of for alternative semiconductors with similar, but complementary interest. Hence, the convergence of i) the outstanding properties graphene-like layered structure features in order to fill the entire of emerging i2DMs, and ii) the limitless variety of molecules that spectrum of electronic properties. can be custom-designed and synthesized with predictable func- Succeeding graphene, the family of 2D materials—defined as tionalities, clearly offers a promising avenue to create stimuli- crystalline materials comprised by few atomic layers with strong responsive i2DMs exhibiting programmable behaviors to ad- in-plane interatomic interactions but weak out-of-plane van der vance in the field of post-Moore electronics. Waals forces—has been worldwide broaden in the last decade In the past five years, a large number of reviews summariz- thanks to their distinct properties (e.g., atomic-level thickness, ing the preparation, characteristics, and potential applications finite bandgap, absence of dangling bonds, wide flexibility, and of 2D materials in general, and i2DMs in particular have been high specific surface area plenty of active sites), which are of reported.[15,45,55–83] Nonetheless, a current gap in the field can be great importance for new-generation nanoelectronics.[14,102–106] clearly identified: the lack of investigation on stimuli-responsive Although more than 100 members have been predicted i2DMs for logical information processing at the molecular level. theoretically, only tens of them have been synthesized This fact can be mainly ascribed to the necessity of integrating experimentally.[80] Amongst the extensive library of 2D ma- robust covalent immobilization approaches for functionalizing terials, including organic 2D materials,[107–115] inorganic 2D i2DMs with ad hoc active molecular moieties. Consequently, a materials (i2DMs, described below), and hybrid organic– review including the remarkable merits of covalently engineer- inorganic 2D materials[16,116–120] (see Figure 1 for illustration), ing stimuli-responsive i2DMs to promote the further develop- this Review is specifically focused on the exploration of i2DMs, ment of the expanding field of molecule-programmable nano- and therefore both organic 2D materials and hybrid organic– electronics is demanded. In what follows, this Review begins inorganic 2D materials are out of the scope. In particular, the with a brief overview of potential i2DMs to be explored, high- family of i2DMs can be basically categorized in four types: lighting their inherent features. Then, different molecular en- 1) 2D elemental analogues of graphene (Xenes),[121,122] 2) 2D gineering approaches—mainly focused on covalent molecular transition-metal chalcogenides,[123,124] 3) 2D transition-metal functionalization methods—to functionalize a la cartè i2DMs carbides/nitrides (MXenes),[34,125] and 4) 2D transition-metal with molecular components will be introduced, paving the bases oxides and hydroxides (TMOs and TMHs).[40,126] In general, to provide a robust molecular immobilization. Next, prominent while Xenes are mainly synthesized via top-down chemical examples of stimuli-responsive molecular and supramolecular approaches (i.e., chemical vapor deposition, CVD), most of the switches triggered by different external inputs (e.g., optical, elec- rest i2DMs can be obtained through a bottom-up exfoliation of trical, thermal, chemical, etc.) will be presented, since they are the their bulk counterparts, resulting in 2D materials made of few source of inspiration of many logical binary applications. Finally, layers with nanosheet morphology.[127] the promising implementation of stimuli-responsive i2DMs in the field of molecule-programmable nanoelectronics will be dis- cussed, pointing out specific examples of bistable molecular 2.1. Elemental Graphene Analogues (Xenes) switches. Overall, it is hoped that this Review could provide a comprehensive strategy for the custom molecular modification Motivated by the possibility of reducing elements beyond car- of i2DMs to expand their integration in the exciting research bon into their graphene-like 2D counterparts, a new family of area of post-Moore devices by implanting the inherent molecu- elemental honeycomb-structured 2D materials known as Xenes lar responsiveness of active molecular components on emerging was born, where X refers to the main group elements rang- i2DMs. ing from Group IIIA to Group VIA, while the Latin suffix “- ene” (meaning sheets) is used to emphasize their layer form 2. Inorganic 2D Materials as an analogy to graphene.[121,128] Xenes were initially designed to expand the family of 2D materials belonging to the Group In the past two decades, carbon allotropes made of hexagonal ar- IVA[129] —viz., silicene (2010),[130] germanene (2014),[131] stanene rangements of sp2 -bonded carbon atoms have led the branch of (2015),[132] and plumbene (2019),[133] —resulting in the 1st gen- Nanotechnology.[84–89] After the discovery of fullerene[90] (0D) and eration of Xenes. To date, the current portfolio of Xenes has Adv. Mater. 2023, 2305546 2305546 (2 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 1. Map of 2D materials formed by 2D organic materials: polymers, covalent-organic frameworks (COFs), organic small molecules (OSMs), and carbon materials (CMs); 2D inorganic materials: elemental analogous of graphene (Xenes), transition-metal chalcogenides (TMCs), transition-metal carbides/nitrides (MXenes), and transition-metal oxides/hydroxides (TMOs/TMHs); and 2D hybrid organic–inorganic materials: metal oxide frameworks (MOFs), hybrid perovskites, and molecular and (supra)molecular hybrids. been extended to fifteen non-graphene Xenes predicted theoret- ture of the element but also associated with its specific atomic ically, where 13 of them have been also created experimentally, arrangement.[60,150,159] Figure 2 illustrates an historical view of with only indiene[134] and aluminene[135] remaining. The ongo- the two generations of Xenes with its corresponding most stable ing 2nd generation of Xenes, which relates the neighboring el- atomic structures. ements of the periodic table adjacent to Group IVA, includes: Group IIIA[136] —borophene (2015),[137] gallenene (2018),[138] and thallene (2020),[139] —Group VA[140] —phosphorene (2014),[141] 2.2. Transition-Metal Chalcogenides arsenene (2018),[142] antimonene (2016),[143] and bismuthene (2017)[144] —and Group VIA[145] —selenene (2017)[146] and tel- Chalcogenides—also known as “ore formers,”[160] coming from lurene (2014),[147] —each of them displaying a large number and the Greek words “chalcos” (ore) and “gen” (formation)—are de- variety of optical and electronic properties to be exploited for fined as a group of inorganic materials and compounds con- different applications.[128,148–156] Unlike the ideally planar hon- taining elements of the Group VIA of the periodic table, in- eycomb structure of graphene due to the sp2 hybridization of cluding sulfur, selenium, and tellurium, but excluding oxygen carbon atoms, Xenes all prefer alternative anisotropic lattice (since oxides have very different chemical behaviors) and polo- structures with alternating degrees of out-of-plane atomic buck- nium (because its radioactivity).[161] Thus, TMCs are related to ling (sp2 –sp2 hybrid) and puckering (sp3 ).[150,157] For example, those i2DMs consisting of at least one chalcogen anion (S2− , borophene cannot form graphene-like stable honeycomb struc- Se2− , and/or Te2− ) and at least one metal cation (which in- ture since B only contains three valance electrons (rather than car- clude some 3d–5d early transition metal elements). TMCs are bon, that contains four), while phosphorene—the lightest stable usually classified with regarding to their number of chalcogen elemental Group—VA Xene—can form five different allotropic ions (e.g., mono-, di- or tri-chalcogenides), being 2D transition- forms, including orthorhombic (black phosphorene) and bucked metal dichalcogenides (TMDs) as MX2 —where M is a transition honeycomb (blue phosphorene) structures.[158] Thus, the physic- metal atom (e.g., Mo, Ti, W, V or Nb) and X is a chalcogenide ochemical properties of Xenes are not only ascribed to the na- atom—the most studied, and therefore explored ones.[31,32,162,163] Adv. Mater. 2023, 2305546 2305546 (3 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 2. A) Periodic table highlighting the synthesized single-element 2D materials (graphene and Xenes) from Group IIIA to Group VIA with its corresponding year of publication. B) Most stable graphene-like atomic structures of Xenes (balls correspond to atoms and lines represent interatomic bonds), also presenting the typical flat honeycomb lattice of graphene (C, Group IVA) for comparison. Adapted with permission.[150] Copyright 2020, Elsevier. Particular attention has been paid to TMDs due to their unique nation with their less covalent nature and low electronegativity, combination of atomic-scale thickness, direct bandgap, and fa- make them excellent candidates for their implementation in a vorable mechanical and electronic features,[164,165] representing wide range of nanoelectronics applications.[30,175–181] an alternative group of 2D materials that compensates, for ex- ample, the intrinsic semimetallic nature of graphene or the in- sulating characteristics of hexagonal boron nitride[166] (h-BN). In 2.3. Transition-Metal Carbides/Nitrides (MXenes) this regard, the inherent characteristics of TMDs are strongly in- fluenced by their composition nature, spanning the entire range The family of the so-called MXenes[184–186] —with a general chem- of electronic structures from semiconductors (e.g., MoS2 ,[167] ical formula: Mn+1 Xn Tx , where M is an early transition metal, X is WS2 [168] ) to semimetals (e.g., WTe2 ,[169] TiSe2 [170] ), true metals either C and/or N, and Tx refers to the surface-terminating func- (e.g., NbS2 [171] ) or superconductors (e.g., TaS2 [172] ). In general, tionality (commonly: ─O, ─OH, and ─F groups)—was first in- the link between TMDs relies on the van der Waals interac- troduced by Gogotsi and co-workers in 2011.[187] Analogously to tions between different covalently sandwiched X–M–X mono- the procedure to obtain layered graphene from bulky graphite, layers (two chalcogenide planes separated by a transition metal they demonstrated the suitability of selectively etching the A- plane) that stacked the bulk 3D crystals—in parallel to the stacked group out of 3D bulk ternary transition metal carbides/nitrides— layers of graphene forming the bulk graphite—, where M can known as MAX phases,[188] being A mostly an element of Group have either octahedral or trigonal prismatic coordination (see IIIA and IVA—by using a fluoride-based chemical (i.e., hy- Figure 3 for illustration). In addition, TMDs can adopt different drofluoric acid, HF) as an exfoliating agent (see Figure 4 for phases or polymorphs, where the preferred one depends upon exemplification). Since then, this family of i2DMs has growth the d-electron count of the transition metal, which is, indeed, a rapidly, with a current library longer than thirty members ex- predominant factor in determining its electrical and conductive perimentally synthesized successfully (e.g., Ti3 C2 ,[189] Ti2 C,[190] properties.[32,173,174] For example, just the MoS2 can exhibit five V2 C,[191] Cr3 C2 ,[192] Nb4 C3 ,[193] Fe2 C,[194] Mo2 C,[195] Hf3 C2 ,[196] different polytypes, such as 1H, 2H, 3R, 1T, and 1T′,[32] where Ta2 C,[197] Cr2 N,[198] Ti4 N3 ,[199] etc.), and dozens more studied the letter initial integer indicates the number of layers in the unit theoretically.[200] cell, while the letter corresponds to the type of symmetry (H, R, The structure of MXenes is based on hexagonal close-packed and T represent hexagonal, rhombohedral, and tetragonal sym- layers of M and X, interleaved one with other, while Tx ac- metry, respectively). Thus, the inherent physicochemical charac- tive groups are randomly distributed on the surface. In this re- teristics of TMDs with regarding the crystal structure, in combi- gard, Tx active groups play a pivotal role in determining the Adv. Mater. 2023, 2305546 2305546 (4 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 3. A) Early transition metal (M) and chalcogen (X) elements from the periodic table forming TMD crystals. B) Metal coordination and common stacking sequences for 1:2 (X–M–X) TMD: H phase (1H, 2H, and 3R) and T phase (1T and 1T′), showing the crystal structure from both top and side views. Adapted with permission.[182] Copyright 2020, Annual Reviews. C) HRTEM image of few layers of MoS2 as a model TMD. Reproduced with permission.[183] Copyright 2016, Elsevier. material properties of MXenes.[203–210] Nowadays, titanium car- tronics, optoelectronics, and/or photonics applications.[39,218–222] bide (Ti3 C2 Tx ) is one of the most widely MXene studied thanks to Both of them can be classified into two main families: i) binary its unique set of properties, including high electrical conductivity and ternary 2D TMOs, referring to those oxides containing ei- and mechanical features, high negative zeta-potential, biocom- ther one or two metal elements in the formula, respectively;[223] patibility, large area-to-volume ratio, good chemical stability, tun- and ii) single and double 2D TMHs, referring to those hydroxides able surface functionality, and efficient absorption of electromag- containing a metal with either a single oxidation state or a mix of netic waves.[34] Such a combination of properties, together with oxidation states, respectively.[224] In general, there are two major the inherent metallic conductivity determined by their free elec- strategies to synthesize both 2D TMOs and 2D TMHs: top-down trons as well as hydrophilicity caused by surface terminations, and bottom-up methods, being the top-down chemical exfolia- makes MXenes as excellent candidates for a large number of na- tion approach the easiest and fastest way for isolating layered ox- noelectronic applications.[185,211–214] In this last regard, the term ides/hydroxides from the parent bulky precursor.[225–227] The ex- MXetronics has emerged to allude to the electronic and photonic tensive variety of different TMOs/TMHs crystal structures is the applications of MXene-based devices.[211,215–217] result not only of the diverse stable valance states of the transi- tion metal constituents, but also of the various crystal phases that some of them present (see Figure 5). 2.4. Transition-Metal Oxides/Hydroxides On the one hand, TMOs are a class of semiconductors that despite being mainly camouflaged by TMCs (probably be- TMOs and TMHs constitute an important class of i2DMs owing cause TMOs exhibit, in general, wider bandgap energies),[228] to their unique layered structures and variable chemical compo- they present a series of benefits, including not only good sitions, being possible to be used for a wide range of nanoelec- electron transport properties that alleviate the fast charge Adv. Mater. 2023, 2305546 2305546 (5 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 4. A) Elements in MAX phases and MXenes. Reproduced with permission.[201] Copyright 2021, Springer. B) Typical synthesis and delamination of MXene from MAX phase via selective etching with its corresponding atomic structures (exemplification of an M3 AX2 phase transformation (e.g., Ti3 AlC2 ) into M3 X2 Tx (e.g., Ti3 C2 Tx ). Table of colors: M: blue, A: red, X: purple, T: gray. C) SEM images representing i) Ti3 AlC2 phase, ii) Ti3 C2 MXene, and iii) delaminated Ti3 C2 Tx MXene. Reproduced with permission.[202] Copyright 2017, Elsevier. recombination characteristic, but also lower synthetic costs and the case of hydrotalcite structures in double 2D TMHs,—with a higher chemical stability in air when compared to that of general formula: {[(M1-x 2+ Mx 3+ (OH)2 ]x+ [Ax/n ]n− ·mH2 O}, where TMCs.[229,230] For example, in nature exists a vast variety of M2+ and M3+ is a divalent and trivalent metal cation, respec- layered TMOs—composed of stacked, negatively charged slabs tively, and An− is a charge-balancing interlayer anion—, those with surrounding alkali metal cations occupying the interlayer brucite-like layers are intercalated one with other through water space—that have been successfully delaminated, as the case of molecules and organic/inorganic anions, forming van der Waals K0.8 Ti1.2 Fe0.8 O4 , KCa2 Nb3 O10 or Cs6+x W11 O36 .[38] The most rep- and electrostatic interactions with the hydroxyl groups of the host resentative example of TMO is TiO2 , but the atomistic structures layers.[238] of the majority of studied 2D TiO2 materials remain still unclear, in which anatase seems to be the most common crystal struc- 3. Molecular Engineering of i2DMs ture in the 2D configuration.[231,232] Nonetheless, the wide optical bandgaps of TiO2 (3.2–3.4 eV) restrict the light absorption only Molecular engineering is becoming a powerful tool in the field of in the ultraviolet region.[233] Thus, the research of 2D TMOs has 2D materials to fulfill the central challenge of materials science: been mainly focused on exploring binary TMOs with bandgap en- the design of materials with programmable functions.[17] The as- ergies in the range of 2.6–3.0 eV to lie in the visible light region, sembly of active molecular components (i.e., stimuli-responsive as the case of MoO3 ,[234] WO3 ,[235] Ga2 O3 ,[236] and V2 O5 .[237] molecules) supposes an excellent opportunity to enrich the func- On the other hand, TMHs are regarded as a novel family tionalities and complement the limitations of i2DMs according of functional i2DMs with outstanding performances as electro- to task-specific applications. The fact of selecting and adapting catalysts and energy systems. The general crystal structures of the active molecular constituent anchored upon the substrate 2D TMHs are brucite-type single or hydrotalcite-type double 2D not only provides a custom way to modulate and/or manipulate TMHs.[226] Both of them are built of octahedral units (slabs) of most of the physicochemical features of pristine i2DMs (e.g., op- brucite-like layers linked by edges, which are constituted by six tical, electronic, and thermal properties), but also helps to control OH- groups placed in the corners of the octahedron, while a di- the interactions between the material and its surrounding envi- valent and/or trivalent metal cation is positioned in the center. In ronment. In particular, molecular functionalization can have a Adv. Mater. 2023, 2305546 2305546 (6 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 5. A) Representative structures of selected single TMO nanosheets whose bulk counterparts are naturally layered. Reproduced with permission.[38] Copyright 2018, Elsevier. B) Basic structure of a double 2D TMH polytype, showing how the interlayer anions and water molecules intercalates the octahedral units of brucite-like layers in a hydrotalcite structure. profound effect on the optical and electrical properties of i2DMs. ods utilize molecular components as building blocks to tune From an optical point of view, one of the most significant effects the physicochemical features of i2DMs, while the nature of of molecularly functionalizing i2DMs is the modulation of their interactions—nonbonded or bonded ones—will depend on the bandgap, leading to changes in their absorption spectra by intro- chemistry of the selected i2DM with the reactive groups from the ducing new electronic states within the band structure.[239] Oth- ligand.[247] erwise, the electrical conductivity of i2DMs can also be modu- lated through molecular engineering, for example, by promoting changes in carrier mobility, shifts in the Fermi level, and even 3.1. Noncovalent Molecular Functionalization of i2DMs doping effects (i.e., n-type or p-type doping) via charge transfer between the i2DM and the anchored molecule.[240] Thus, by im- Noncovalent functionalization approaches rely on nonbonding planting foreign active units, further possibilities are enabled to interactions between the selected i2DM with the molecular com- cover the current gap in i2DMs due to the acquisition of pro- ponent via weak physical adsorption, being the stabilization grammable molecular features.[241] forces involved strong enough to overcome entropic factors driv- Besides the impressive inherent features demonstrated by ing disassembly. The major noncovalent phenomena in i2DM the aforementioned families of i2DMs, a main bottleneck molecular functionalization are usually manifested as i) van der that hinders the proper implementation of i2DMs in the Waals interactions (referring to weak distance-dependent non- field of nanoelectronics can be clearly identified: the lack ionic forces),[248] ii) dipolar interactions (involving electrostatic of sound functionalization strategies to anchor ad hoc active forces),[249] iii) charge transfer interactions (occurring across (supra)molecular components upon i2DM substrates for tuning electron donor–electron acceptor systems),[250] and iv) H-bond their (opto)electronic properties.[242,243] The controlled prepara- interactions[251] (an special type of dipolar interaction that takes tion of robust molecule-rich i2DMs might provide a valuable path place between neighboring H atoms and a highly electroneg- to reach stimuli-responsive i2DMs performing reproducible and ative atom, such as N, O, or F). Briefly, noncovalent molecu- quality electrical characteristics, a must toward the development lar approaches have the advantage of retaining the crystal struc- of complementary-logic devices and circuits. Indeed, the bene- ture of i2DMs unaltered, fact that preserves the (opto)electronic fit of integrating stimuli-responsive molecules as active building properties of the pristine material.[17] Nonetheless, such weak in- blocks upon i2DMs is that programmable nanoelectronics can teractions usually lead to molecule desorption during the task- be reached, since the electronic properties can be modulated re- specific application, a fundamental drawback that hinders its versibly. proper implementation toward the monitoring of bistable molec- In general, two main categories arise when thinking about ular switches. Following the scope of this Review and considering the different ways of interfacing i2DMs with active molec- that a strong molecule–material interaction is a must to provide ular components, which relate to noncovalent[244] and cova- efficient molecular switches, noncovalent molecular approaches lent functionalization methods[245,246] (vide infra). Both meth- have been excluded of revision. Adv. Mater. 2023, 2305546 2305546 (7 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de 3.2. Covalent Molecular Functionalization of i2DMs Amongst the different family of Xanes, germanane derivatives are the most explored one.[261–263] By following the aforemen- Covalent molecular approaches relate to the formation of a tioned methodology, Jiang et al. established the role of tailoring chemical bond between the ligand identity (i.e., active molec- the ligand group anchored to germanane (with regarding its size ular components) and the skeleton of i2DMs.[252] Such chemi- and electronegativity) on modulating the electronic structure of cal bonding can occur either directly into the i2DM sheets or Xanes (Figure 6B).[260] Indeed, the fact that the bandgap of ger- indirectly through the functional groups exposed on the sur- manene can be easily tuned by the tethered ligand has increased face of some i2DMs. In general, the covalent functionaliza- the interested in developing alternative functionalization meth- tion of i2DMs via wet-chemical approaches allows for molec- ods to widen the library of 2D-GeR derivatives in order to advance ularly binding on both sides of the plane.[253] The main ben- toward the development of versatile and robust synthetic meth- efits of anchoring molecules to i2DMs via strong bonding in- ods capable of customizing Xanes with the desired molecular teractions are: i) enhanced stability (the covalent bond ensures component; for example, by the inclusion of Grignard reactions that the molecular component will remain anchored to the on previously synthesized 2D-GeI (Figure 6C),[264] or by click- i2DM during device operation, preventing molecular desorp- ing thiol-rich molecular components upon 2D-GeCH2 CH═CH2 tion), ii) control over molecular orientation (crucial to under- via a thiol–ene click reaction (Figure 6D).[18,120] In this last re- stand the mechanism behind the molecular switch), iii) long- gard, Muñoz et al. also exploited this click approach to reach term durability (longer operational lifetime is expected owing organic–inorganic 2D-germanene heterostructures by covalently to the strong and stable covalent bond), iv) reduced molecule– anchoring thiol-rich carbon dots.[120] Further germanene func- molecule interactions (preventing undesirable interference sig- tionalization approaches have been recently summarized by Ng nals and therefore, enhancing device performance), and v) large- and Pumera[265] and Hartman et al.[266] Regarding to the family scale manufacturing (covalent molecular functionalization can of silicanes, the so-called siloxene—[SiH1-x (OH)x ], whose struc- be adjusted to mass production, simplifying the manufacturing ture is terminated with ─H and ─OH ligands—is probably the of molecule-programmable nanoelectronics with reproducible most exploited one.[267] Beyond the general topotactic transfor- electronic performances). However, since covalent bonds are ir- mation of Ca2 Si with halide acids, a direct chemical synthesis reversible and permanently modify the material surface, the per- of benzyl-modified silicane has been successfully achieved from fect structure of i2DMs can be significantly affected, and there- bulky Ca2 Si.[268] Comparing to silicane and germanane deriva- fore the electronic and structural characteristics of i2DMs can be tives, the synthesis of stanane derivatives (SnR) is almost an un- disrupted.[254] explored field, fact that can be ascribed to the propensity for oxi- What follows briefly addresses the main types of covalent in- dation of its crystalline Zintl phase precursor (BaSn2 ).[269,270] teractions that may be promoted when exposing i2DMs to small Regarding to alternative Xenes, Group-V Xenes, such as phos- organic molecular components with regarding the nature of the phorene and arsenene have been successfully covalently func- selected i2DM. tionalized with different molecular moieties by different chem- ical methods. On the one hand, the chemistry of black phospho- rus offers two main covalent functionalization routes, as shown 3.2.1. Covalent Functionalization of Xenes in Figure 7: the direct formation of P─C bonds via either diazo- nium salts[271] (Figure 7A) or nucleophilic attack of P groups,[272] The lack of stability of Group IV-Xenes (viz., germanene, silicene, and the indirect formation of P─O─C bonds by taking advan- and stanene) under ambient conditions makes them as ideal 2D tage of the reactivity of the ─OH groups present on its surface systems to understand the pivotal role of surface functionaliza- (owing to its oxidation with air) with nucleophilic reagents.[273] tion, since the inclusion of a ligand termination on each atom Alternatively, the use of aryliodonium salts has shown to pro- is a must to reach stable i2DMs.[255–257] This has resulted in a vide both P─C and P─O─C bonds, resulting in a greater cova- subclass of Xene-based derivatives known as Xanes (e.g., silicane, lent functionalization (Figure 7B).[274] On the other hand, the germanane, and stanane), where the suffix “-ene” is replaced by“- chemistry of gray arsenic has been mainly limited to the reac- ane” to point out the inclusion of ligand-terminated groups via tivity through the nonbonding electron pairs of As, which allows single bonds ending, analogously to graphane.[258] coordination with organometallic compounds (e.g., [Cr(CO)6 ] via In general, Xanes are obtained by a specific type of direct solid- UV irradiation),[275] as well as As═C bond formation with reactive state chemical approach known as topochemical reaction, which carbene-based species (Figure 7C).[276] transpires under the strict control of molecular packing in the crystal lattice.[259] This approach is based on the topotactic trans- formation of bulkier Zintl phases—the intermetallic-layered pre- 3.2.2. Covalent Functionalization of TMCs cursor made of M2 X, being M an alkaline earth metal (i.e., Ca or Ba) and X the Group IV element—into covalently terminated The covalent molecular functionalization of TMCs in gen- XR–Xanes (viz., SiR, GeR, and SnR) upon the reaction with either eral, and TMDs in particular, can be mainly summarized in halogen acids or haloalkanes in aqueous media, where the termi- four chemical approaches (see Figure 8): i) thiol-based molec- nal R ligand (R = ─H or alkyl group, such as ─CH3 , CH2 OCH3 , ular chemisorption via vacancy engineering,[277–279] ii) direct and ─CH2 CH═CH2 , respectively) covalently bonds each p-block S─C bond formation using reactive diazonium salts,[280] iii) X atom.[255] Figure 6A exemplifies the general topochemical dein- thiol–Michael click addition,[281] and iv) nucleophilic reactivity tercalation mechanism to transform bulkier Zintl phases into through phase transition engineering,[246] where the proper func- molecule-rich Xene crystals. tionalization strategy is highly influenced by the crystal phase of Adv. Mater. 2023, 2305546 2305546 (8 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 6. A) Schematic of the topochemical deintercalation of Zintl phases, such as Ca2 Ge or Ca2 Si, with R halides (R = H or alkyl chains) to reach silanene and germanane derivatives (Xanes). B) E2 Raman shifts in ten different GeR derivatives plotted as a function of their absorption on- sets (bandgaps). Reproduced with permission.[260] Copyright 2016, American Chemical Society. Alternative functionalization of previously synthesized C) 2D-GeI via Grignard method, and D) 2D-GeCH2 CH═CH2 via thiol–ene click chemistry. the pristine TMD. What follows describes the different chemi- vantage of the high binding affinity of 1,2-dithiolenes toward S- cal approaches to covalently tether a wide variety of molecular vacancy-based Mo atoms, particularly those located at the edges components onto TMDs, using MoS2 as a model TMD; however, of the i2DM. Overall, vacancy engineering is a facile molecular these methods can be simply extended to additional TMDs (e.g., functionalization strategy, which offers the advantage of keeping WS2 and MoSe2 ). intact the basal plane of MoS2 , while preserving their semicon- First, vacancy engineering is probably the most exploited ap- ducting character. proach for covalently tethering small molecules onto the sur- Second, an additional approach for covalently anchoring or- face of 2H-MoS2 . Briefly, the 2H phase is the most thermody- ganic molecules on unmodified 2H-MoS2 is through a radical- namically stable form of MoS2 , which exhibits a semiconduct- mediated reaction utilizing diazonium salts, where a robust S─C ing nature but an almost inner reactivity. Thus, a simple way bond can be formed triggered by the presence of S-vacancies to modify 2H-MoS2 is by taking advantage of its naturally oc- that serve as nucleation centers for the initial functionalization curring sulfur vacancies (SV) in its lattice during chemical ex- (Figure 8B).[286] The mechanism proposed follows three sequen- foliation, where thiol-rich molecules can spontaneously occupy tial steps: 1) rapprochement of the diazonium salt derivative (R′– those defects by following the reaction: [R′–SH + SV–MoS2 → Ar–N2 + ) upon the i2DM surface, where 2) a surface charge re- R′–S@MoS2 (H)] (Figure 8A).[282,283] Importantly, this particular arrangement allows the N2 group to break off, forming a radical functionalization approach well preserves the physical structure group (R•) that promotes 3) a covalent C─S bond formation. This of the resulting molecule-rich TMD. Nonetheless, some compu- strategy has shown to be very useful for molecularly engineering tational works cast doubt on the resultant products and reaction not only different TMCs (e.g., MoS2 , WS2 , MoSe2 , and WSe2 ), but mechanisms, demonstrating that other subproducts via repair- also alternative TMDs, such as Bi2 S3 and Sb2 S3 .[287] For example, ing pathway ([R′–SH + SV–MoS2 → MoS2 + R′–H]) and dimer- Miller et al. demonstrated the suitability of modulating the work ization pathway ([2R′–SH + SV–MoS2 → (R′–S)2 + MoS2 (H─H)]) function of MoS2 by tailoring the terminal R′ group of the cova- can also be considered.[284] Beyond thiol-rich molecules, Canton- lently grafted aryldiazonium salt, resulting in a reduction or in- Vitoria et al. also demonstrated the suitability of covalently an- crease of the work function when employing electron-donating choring 1,2-dithiolenes on MoS2 nanosheets.[285] As validated or electron-withdrawing R′ groups, respectively.[288] by density functional theoretical studies and material character- Third, the thiol–Michael addition reaction—included into the ization experiments, this functionalization occurs by taking ad- click chemistry toolbo[289] —has also been successfully exploited Adv. Mater. 2023, 2305546 2305546 (9 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de azonium salts.[294] In addition, phase engineering was also ex- ploited for covalently synthesizing a modified 1T-MoS2 with ter- minal phenylazido pendant arms, which was further post-treated with terminal acetylene derivatives via copper-mediated azide– alkyne cycloaddition, a click chemistry alternative to further wide the library of molecule-rich TMDs.[295] 3.2.3. Covalent Functionalization of MXenes Contrary to Xenes and TMCs, the covalent functionalization approaches for anchoring ligands upon MXenes is mainly fo- cused on exploiting the reactive groups (Tx ) exposed on its surface,[296,297] which will also depend on the type and fraction of Tx during production.[298] Such particularity endows MXenes with negative charged characteristic and high surface activity, opening up a wide range of chemical strategies for molecularly engineering MXenes with ad hoc molecular components. Tak- ing into account that the main reactive groups exposed on MX- enes are both halogens and oxygenated groups,[299] the former (Tx = halogen groups) allows for noncovalent modification ap- proaches (i.e., H-bonds[300] and electrostatic assembly[301] ), while the latter (Tx = oxygenated groups) makes also possible the im- plementation of covalent methods.[297,302] Consequently, exploit- ing the high reactivity of the different oxygenated groups (e.g., ─O─, ─OH) is the most primary and direct approach for cova- lently functionalizing MXenes. On the one hand, the presence of oxygenated groups allows to implement chemical methods sim- Figure 7. Proposed mechanisms for the covalent molecular functional- ilar to the ones carried out on 2D graphene derivatives (i.e., re- ization of Group-V Xenes, such as i) black phosphorous via A) direct P─C duced graphene oxide).[303–305] On the other hand, the fact that bond formation (exemplification using diazonium salts) and B) indirect P─O─C bond formation (exemplification employing an iodine-based nu- the transition metal core is directly connected to Tx makes it pos- cleophilic reagent), and ii) gray arsenic via C) chlorocarbene-mediated sible to see MXenes as MO2 -like structures, and therefore the As═C bond formation. chemistry to carry out will be close to the one for functionalizing TMOs (ut infra). Consequently, four main covalent molecular ap- proaches for functionalizing MXenes can be considered: i) self- for anchoring maleimide derivatives onto 2H-MoS2 (Figure 8C). assembling of silanes via Ti─O─Si bond formation,[306] ii) self- In this case, the soft nucleophilicity of S atoms allows the click assembling of phosphonates via Ti─O─P bond formation,[307] iii) integration of the molecular components through a Michael ad- nucleophilic substitution via Ti─O─C bond formation,[217] and dition under very mild conditions.[281] This method has been iv) diazonium salts grafting via radical-induced Ti─O─C bond particularly appealing for the Pérez’s group, since further click formation.[308] Figure 9 summarizes these four main covalent chemistry approaches have been explored, for example, for ei- strategies, using Ti3 C2 Tx as a model MXene material. ther the covalent cross-linking of different flakes of 2H-MoS2 Self-assembling has shown to be a versatile strategy for through bismaleimide reagent,[290] the linkage of graphene to covalently anchoring a wide range of molecular components reach 2D/2D heterostructures,[291] or the formation of succin- via either silylation[306] (Si(OR)3 –R′) or phosphorylationf[307] l imide polymer adlayers covalently connected to 2H-MoS2 by (PO(OR)2 –R′) process, where OR corresponds to hydrolysable adding a basic reagent (rather than the molecular monolayer of groups and R′ stands for an aliphatic chain carrying a ter- maleimide clicked in absence of base).[292] minal functional group. As shown in Figure 9A,B, the driv- Lastly, a fashionable way to overcome the inherent inner reac- ing force of these two chemical approaches relies on a spon- tivity of 2H-TMD—mainly attributed to its neutral charge state taneous condensation dehydration between the ─OH groups that difficult electron transfer—is by employing the so-called from MXene and the OR hydrolysable groups (R = H or alkyl phase transition engineering approach.[246,293] This method relies groups) from the coupling agents via esterification/etherification on converting the semiconducting 2H phase onto the metallic 1T process,[309] leading to the formation of a new chemical one using n-butyllithium, in which its intercalation promotes a bond (i.e., Ti─O─Si or Ti─O─P). In addition to the result- partial conversion of the crystal structure via electron transfer, re- ing chemical bond formation, further noncovalent interac- sulting in a negatively charge 1T-TMD nucleophile-like structure tions like H-bond interactions can also be promoted.[310] This allowing the integration of electrophiles, such as alkyl halides method is simple and makes it possible the inclusion of dif- and aryldiazonium salts (Figure 8D). Recently, Chen et al. have ferent R′ terminal groups. For example, Bagheri et al. demon- reported a synthetic strategy for the simultaneous bisfunction- strated the suitability of reacting Ti3 C2 Tx MXene with a mix alization of MoS2 sheets employing both organohalides and di- of two different types of silanes, such as (3-aminopropyl) Adv. Mater. 2023, 2305546 2305546 (10 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 8. Proposed mechanisms for the covalent molecular functionalization of TMDs (e.g., MoS2 and WS2 ) via A) vacancy engineering, B) direct S─C bond formation with reactive diazonium salts, C) thiol–Michael click addition, and D) phase transition engineering. triethosysilane and (3-mercaptopropyl) trimethosysilane, for the new Ti─O─C bond. Briefly, the highly negative Zeta potential of inclusion of more than one chemical group (i.e., amine and thiol MXenes provides them with free electron clouds that guarantee groups[311] ) during the same procedure. This is especially ap- the grafting of diazonium salts.[318] pealing since the R′ terminal groups can be utilized for further Finally, it is important to highlight that less-frequently molec- functionalization.[312] ular covalent functionalization on MXenes have also been re- Beyond silylation and phosphorylation, other type of organic ported, as the case of 1) the direct Ti─N bond formation on molecules (e.g., catechols,[313] carboxylic acids,[275] or isocyanate Ti3 C2 Tx –MXene with glycine[319] or 2) the direct in situ forma- groups[314] ) can be anchored on Ti3 C2 Tx –MXene via nucleophilic tion of metal nanoparticles (M-NPs, such as Ag-NPs and Au-NPs) substitution, resulting in a new Ti─O─C bond formation. On on Ti3 C2 Tx –MXene using a metal ion precursor (Mn+ ),[320] which the one hand, carboxylic acids and catechols are grafted on they are used as nanotemplates for the incorporation of thiol-rich MXenes through an esterification process (catalyzed by pro- molecules via M─S bond formation.[321] tons) followed by a dehydration reaction.[315] In general, the functional reactive groups of the selected molecular compo- nents are previously protonated in acidic media solution (e.g., 3.2.4. Covalent Functionalization of TMOs/TMHs ─C─OH2 + , ─C═OH+ ), resulting in an electrophilic carbon that can be attacked by the nucleophilic MXene rich in surface- As mentioned above, the chemistry of TMOs will be very terminating ─OH groups, with subsequent removal of H2 O similar to the one utilized for MXenes owing to their MO2 - (Figure 9C).[217,316] On the other hand, a carbamation process oc- like structure. In general, metal oxides react with air, form- curs when MXene is exposed to isocyanate groups in presence of ing surface-bonding hydroxyl groups that favor reactivity with a tertiary amine, which plays a fundamental role to catalyze this a wide variety of reactive groups in solution,[322] including reaction.[317] silanes,[323] phosphonates,[324] carboxylic acids,[325] diazonium Otherwise, diazonium salts derivatives (e.g., aryldiazonium salts,[326] catechols,[327] alkynes/alkenes[328] or thiols,[329] as de- salts) have also demonstrated its suitability not only for provid- picted in Figure 10. In parallel, same approach can be thought ing covalently bonded TMCs, but also MXenes (Figure 9D).[313] when using TMHs, since their ─OH groups play a pivotal role In general, this strategy relies on in situ forming the diazonium in surface modification.[330] Nonetheless, taking into account that salt derivative by reacting a primary amine with nitrous acid. Af- the implementation of both 2D TMOs and 2D TMHs is still in an terward, the resulting diazonium salt releases N2 (g) derived from early stage, their covalent functionalization with molecular com- the acquisition of an electron from the MXene surface, inducing ponents is almost an unexplored field, and therefore there is still the formation of a reactive free carbon radical that gives rise to a plenty of room to explore.[331] Adv. Mater. 2023, 2305546 2305546 (11 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 9. Proposed mechanisms for the covalent molecular functionalization of MXenes (e.g., Ti3 C2 Tx –MXene, being Tx = ─OH groups via A) silylation, resulting in a Ti─O─Si bond formation, B) phosphorylation, with the corresponding Ti─O─P bonding, C) nucleophilic substitution, resulting in a new Ti─O─C chemical bond, and D) radical-induced Ti─O─C bond formation using diazonium salts derivatives. The covalent functionalization of TMOs/TMHs using silanes the feasibility of the chemical bond. Additionally, Atanasova et al. (Si(OR)3 –R′) and phosphonates (PO(OR)2 –R′) coupling agents reported the direct M─S bond formation on ZnO–TMO us- through self-assembling is probably the most explored route ing azide-functionalized thiol linker molecules.[336] Regarding for anchoring molecular moieties, since it allows for a rapid to 2D TMHs, Dou et al. covalently anchored a catecholate lig- and spontaneous formation of a robust molecule–TMO/TMH and (i.e., dopamine) upon 2D Mg/Al-TMH—which was subse- linkage,[332] resulting in a new chemical bond (i.e., M–O–Si or quently modified with a copolymer (i.e., poly(methyl vinyl ether- M–O–P). In addition, the reactive R′ group can be further uti- alt-maleic anhydride) by conjugating the anhydride groups of the lized for additional chemical modifications. For transition metal copolymer to the amine groups of dopamine—for the prepara- oxides like TiO2 and ZrO2 , phosphonates have proven to be tion of a mussel-inspired layered double hydroxide material for more stable than silanes in the pH range of 1–10.[333] Moreover, the removal of copper ions.[337] Zeininger et al. provided a toolbox to identify optimal monolayer- surface combinations on TiO2 surfaces exploring different bind- 4. Stimuli-Responsive Molecules Triggered by ings with phosphorous, carboxylic acids, and catechol ligands, Different External Inputs demonstrating that phosphonic acids were preferable compared to catechols and carboxylic acids.[334] Additionally, alternative co- In recent years, the materials science community has evolved valent approaches have been reported for 2D TMOs. For example, from passive to active materials.[53,338–341] While the properties Zhong et al. covalently interfaced 2D TiO2 –TMO with oxidized of passive materials cannot be modified postsynthesis, those of graphitic C3 N4 molecules via Ti─O─N binding.[335] Although ex- active materials can be modulated by simply applying an ex- perimental characterization did not really evidence the covalent ternal stimulus. In general, external stimuli can be of i) phys- nature of the anchoring, DFT calculations clearly demonstrated ical (e.g., light, electrical bias, temperature, ultrasounds, force, Adv. Mater. 2023, 2305546 2305546 (12 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 10. Main covalent molecular approaches for functionalizing TMOs and TMHs with molecular components by taking advantage of the ─OH groups exposed on the i2DMs’ surface. magnetic field, etc.) or ii) chemical (e.g., pH, ions, supramolec- particular change on the anchored material, and the specific task ular host–guest interactions, biochemical agent, redox species, application.[380] Some of the advantages of implanting molecu- etc.) origin.[342–345] In this regard, molecular engineering has al- lar switches on materials/surfaces relies on i) high precision de- lowed the development of responsive materials, which result sign at the molecular level, ii) low energy operando, iii) rapid re- from the confinement of active molecular and supramolecular sponse time, and iv) tunability and reversibility of the optoelec- components upon materials that act as bistable switches.[346] Ac- tronic properties. However, it can also involve some drawbacks, tive molecules can respond to changes in their environment; con- such as i) limited operating conditions, ii) short-term stability sequently, the translation of a molecular change—triggered by (durability), iii) costly large-scale production (scalability), and iv) an external input—into a readable output signal can be achieved. versatility for different applications. Bistability refers to the existence of two or more thermodynam- What follows summarizes prominent examples of molecular ically (meta)stable states in a single system, capable of being re- components displaying bistable active forms in solution when versibly interconverted between them in response to an external they are subjected to different external triggers, a key aspect to stimulus.[347] This fact influences the system depending on the consider when engineering stimuli-responsive materials in gen- state, and therefore allows the possibility of reading out the sys- eral, and stimuli-responsive i2DMs in particular. tem as binary logic data (0, 1). Thus, molecularly engineering of stimuli-responsive materials by implanting the inherent active characteristics of active molecules represents an efficient path- 4.1. Molecular Switches Triggered by Physical Inputs way toward processing binary logic operations at the molecular level. Physical stimuli-responsive molecules displaying bistable molec- Active molecules responding to externally applied physical ular switches in solution can be classified in three main families: or chemical stimuli, have shown to be very promising for i) light-responsive molecules, ii) redox-responsive molecules, and developing a wide variety of stimuli-responsive materials act- iii) temperature-responsive molecules. ing in a controllable and predictable fashion (programmable properties), such as polymers,[348–352] nanocarriers,[353–358] 2D materials,[359–364] supramolecular macrocycles,[365–368] micro- 4.1.1. Light-Responsive Molecules /nanomotors,[347,369,370] 3D printed platforms[54,371–375] or solid substrates,[376–379] amongst other. The selection of a stimulus will Light-responsive molecules have the ability to transform light depend on the characteristic of the molecular component (sen- energy into intelligent molecular functions encoded in the sitivity to a specific type of stimuli), its capability to promote a form of wavelengths, promoting significant macroscopic Adv. Mater. 2023, 2305546 2305546 (13 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 11. Prominent examples of light-responsive molecules to be anchored on i2DMs with their corresponding photoisomers. A) Azobenzene, B) stilbene, C) spiropyran, and D) diarylethene derivatives. effects.[381] Light-driven bistable molecular switches—so- 4.1.2. Redox-Responsive Molecules called photoswitches—are based on a phenomenon known as photochromism, which can be defined as a reversible struc- The main characteristic of molecular switches driven by an ex- tural transformation of the molecular skeleton induced by ternal electrical bias is that the molecular moiety must con- light irradiation that provides two different molecular forms tain an electrically active group capable of undergoing con- (photoisomers).[382] The resulting photoisomers exhibit not only formational and/or chemical changes once the electrical input different absorption spectra, but also physicochemical changes is received.[392] For this type of molecular switches, two main (e.g., geometry, rigidity, dielectric constant, etc.), which are, groups of molecules can be considered: i) electrochemically re- indeed, those physicochemical changes utilized to read out the dox active molecules and ii) electrochemically nonredox active system as two distinct states in a molecular binary logic element. molecules. In general, the main types of transitions of photoswitches rely on Regarding to redox active molecules, they have the partic- i) Z/E or cis/trans isomerization, ii) ring-opening/ring-closing, ularity of possessing a redox active group capable of under- and iii) ring-flipping. going an electron transfer by adding or removing electrons, Amongst the wide variety of photoresponsive molecules fact that can alter the electronic, optical, and magnetic prop- presenting bistability in aqueous environments, derivatives erties not only of the molecules, but also their ensembles.[393] of azobenzene,[383,384] stilbene,[385,386] diarylethene,[387] and Electron transfer, referred to as redox reaction, involves a pro- spiropyran[388,389] are probably the most exploited ones. cess in which a species can either gain an electron leading to Figure 11 illustrates the chemical formula and the reduction (n-type or electron–acceptor species) or, conversely, photoinduced conformational changes of the selected release an electron to become oxidized (p-type or electron- photoisomers. donating species). Although redox-responsive molecules are typ- On the one hand, derivatives of azobenzenes (Figure 11A) ically driven by a physical stimulus (e.g., voltage), they might and stilbenes (Figure 11B) undergo a change in their confor- also be triggered by the action of a chemical agent (named as mation from the most stable E-isomer form to the thermody- oxidants/reductants). Focused on physically stimuli-responsive namically unstable Z-form under UV light irradiation, whose in- electrochemically active molecules, the bistable molecular switch version equilibrium can be reversed upon visible light irradia- is obtained once the electrical bias enters the redox region, tion. On the other hand, diarylethenes (Figure 11C) and spiropy- fact that usually alters the density charge of the molecular rans (Figure 11D) are another class of light-responsive molecules component, resulting in two or more distinguishable electrical whose irradiation by modulating the light source induces a re- states.[54,394,395] Some eminent examples of electrochemically re- versible ring opening and closing, promoting important physic- dox active molecules are derivatives of tetrathiafulvalene,[396,397] ochemical changes. ferrocene[398,399] (and other metallocenes), anthraquinone,[400,401] Alternatively, some nonplanar molecules like helix-shaped benzodifuran[402] or viologen[403,404] (Figure 12A), as well as more molecules (e.g., cethrene[390] derivatives and sterically over- sophisticated molecules such as redox-active proteins,[405,406] crowded alkenes[346] ) are capable of reversibly promoting a helical transition metal complexes,[407] macrocycles,[408,409] and metal– twist driven by a light source, which may result in a chiral inver- organic frameworks.[410,411] It is also worth to mention elec- sion due to the disruption of symmetry (chiroptical switch). Fi- trochromic molecules (or electrophores), a specific type of nally, a recent work published by Gerwien et al. reported an eight- redox-responsive molecules that can reversibly generate op- state molecular sequential switch through controlled rotations tical variations (e.g., color, fluorescence, transparency) in re- around three adjacent covalent bonds by alternating between sponse to an external bias potential, highlighting Prussian blue photochemical Hula-Twist isomerizations and thermal single- (hexacyanoferrate),[412] diimides,[413] and viologens,[414] being the bond rotations, demonstrating that one single molecule can pro- latest the only electrochromic organic molecule exploited in com- mote eight different bistable forms.[391] mercial applications so far. Adv. Mater. 2023, 2305546 2305546 (14 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de delivery.[420] In general, molecular engineering has made it pos- sible to devise thermally responsive materials (usually polymers) by selecting the molecular unit (e.g., monomers, reactive groups) that will mainly promote either a phase transition or a bond conversion into the system. There are several parameters that can be tuned to manipulate the temperature responsiveness, in- cluding molecular structure, functional groups, concentration, and/or hydrophilic–lipophilic balance.[421] A large variety of syn- thetic (and also natural) molecular components have been uti- lized for temperature-responsive assemblies, which mainly in- clude i) copolymers and ii) small organic molecules. Several monomers display thermosensitivity once they poly- merize, leading to a reversible structural phase transition driven by temperature change.[422,423] In general, as temperature is in- creased, the degree of hydrogen bonding between the thermal- stimuli moiety and water decreases, leading to a phase separa- tion. Probably, the main term to take into in mind when se- lecting a thermoresponsive molecular moiety is its lower (or upper) critical solution temperatures, fact that can promote re- versible desolvation (or solvation) upon working at temperatures below (or above) its critical transition temperature. These tran- sitions may induce changes to their specific volume, mechani- cal properties and physical state, resulting in distinctive macro- scopic states.[424,425] Briefly, thermoresponsive polymers made of N-substituted acrylamide monomeres are one of the most stud- ied polymers exhibiting lower critical transition temperatures— especially poly(N-isopropylacrylamide) (PNIPAM), presenting a phase transition at 32 °C in aqueous solutions—,[426] while derivatives of sulfobetaine, such as polysulfopropylbetaine methacrylate and polysulfobutylbetaine methacrylate, present Figure 12. Representation of some stimuli-responsive molecules that upper critical transition temperatures.[427] could be grafted upon i2DMs to be triggered by an external electrical bias. Examples of A) redox active and B) nonredox active molecules. Otherwise, it is known that some light-responsive molecu- lar switches cannot be only erased (reversed) by light, but also with the help of an external thermal stimuli (heating), fact Otherwise, some nonredox active molecules can also modify that usually leads to a thermal isomerization reaction. This is the electron transport when exposed to an electric field; nonethe- the case, for example, of azobenzene[428] and spyropyran[429] less, that kind of switches are typically promoted in solid state, but derivatives (see Figure 11) through a bond conversion, as well not in solution. 4,4′-bipyridine and 1,4′-benzenedithiol,[415] meta- as overcrowded alkenes[430] through a thermal helix inversion oriented diphenyl benzene[416] and thiophene[417] derivatives rep- process. resent some examples of molecules exhibiting a particular phe- nomenon known as antiresonance features of destructive quan- tum interface, where changes in the molecular orbital energy lev- 4.1.4. Alternative Physical Stimuli-Responsive Molecules els relative to the electron Fermi level occurs after applying an external bias voltage, rather than carrier densities as in electro- Besides the aforementioned stimuli-responsive molecules, force chemically redox active molecules.[416] Another interesting type and ultrasounds are another two types of physical inputs that of electrochemically nonredox active molecule exhibiting bista- can promote significant changes on molecules; however, they bility is the one reported by Liljeroth et al., who reported the tau- are rarely used for reading electronic outputs from molecular tomerization of two hydrogen atoms in the inner cavity of naph- switches. thalocyanine molecules.[418] Tautomerization occurs when the Force-responsive molecules are those that can exhibit a chem- two inner hydrogen atoms migrate in the framework of the cav- ical (e.g., formation of a dipole moment or chemical bond ac- ity consisting of four nitrogen atoms (Figure 12B). This change tivation/breakage) or physical shape change upon mechanical is formally equivalent to the rotation of the molecule by 90°, pro- stress, such as compression, tension, pressure or shear. Promi- moting a substantial change in the tunneling current measured. nent examples of mechanochemical molecules are spiropyrans— Similar behavior was found for porphyrin molecules.[419] activated into merocyanine by force—,[431] dioxetanes,[432] and diarylbibenzofuranones.[433] Nonetheless, it is important to point 4.1.3. Thermal-Responsive Molecules out that breaking bonds usually lead to irreversible processes. From an electronic point of view, molecular assemblies formed by Thermal-stimuli systems have recently gained great interest amino acid-based derivatives are of special interest in the field of in the development of biocarrier vehicles for controlled drug piezoelectronics,[434,435] since the induction of a dipole moment Adv. Mater. 2023, 2305546 2305546 (15 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de formation triggered by mechanical loads favors an electrically containing more than one pH-responsive group (e.g., amino readable molecular switch. acids like tryptophan, aniline, etc.) can be protonated and/or de- Acoustic waves are a type of mechanical vibration that propa- protonated by modulating the pH owing to the presence of both gates through a medium by causing the compression and rarefac- a carboxylic acid and amino group,[452] making it possible to de- tion of matter.[436] Briefly, sonosensitizer is the term commonly velop more complex systems. utilized to describe ultrasound-responsive molecules/materials, Beyond protons and hydroxide ions, other molecular architec- which can produce reactive oxygen species when exposed to tonics are susceptible to reversibly interact with other type of ultrasounds. Most of the molecular sonosensitizers are based ions (e.g., alkali metals, alkaline earth metals, transition met- on photosensitizers, including porphyrins, xanthenes, phenoti- als or halides).[453] For example, calix[4]pyrroles represent an ex- azines, and curcuminoids.[437] Although attractive, ultrasound- cellent model of anion receptor systems, in which their confor- responsive molecules generally present poor water solubility mation can be switched from a more stable 1,3-alternate to a and/or phototoxicity. higher energy cone upon complexation with anions.[454–457] In addition, as demonstrated in a photoresponsive TMH function- alized with a 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) 4.2. Molecular Switches Triggered by Chemical Inputs molecular unit, this molecular component can interact with some hazardous metal ions (e.g., Cd2+ ), whose interaction Chemical inputs are associated to those molecules that can in- can be reversed by the addition of a chelating agent as the teract/respond to an external chemical or biochemical agent EDTA.[458] to promote a readable macroscopic change. In general, chem- ically stimuli-responsive molecules promoting bistable molec- ular switches can be summarized in two major families: 4.2.2. Supramolecular-Responsive Host–Guest Systems i) molecules responding to chemical agents, including pH- responsive molecules and other ions beyond hydrogen ions Host–guest motifs are likely the most recognizable mani- (H+ ) and hydroxide ions (OH− ), and ii) electrochemically active festation of supramolecular chemistry. Supramolecular host– molecules suitable to be oxidized or reduced in the presence of guest systems involve two molecular components (viz., host an oxidant or reductant agent (viz., redox-responsive molecules, and guest molecules), which display a noncovalent interac- see Section 4.1.2). In addition, this section also includes another tion (e.g., H-bond, 𝜋-stacking or hydrophobic interactions) to type of chemical stimuli, concretely supramolecular-responsive form a supramolecular inclusion complex.[459,460] Regarding to host–guest systems, where bistable molecular switches are pro- supramolecular-responsive host–guest systems, the main host moted upon the cavity of a supramolecular recognition agent; molecules explored are those based on macrocyclic molecules nonetheless, it is important to point out that the resulting host– containing inner cavities, which can act as container-shaped cavi- guest supramolecular complexes must be switched by the action tands to entrap suitable active (guest) molecules according to the of an additional external physical or chemical stimulus. “lock and key” principle.[461] Then, the supramolecular switch is driven by taking advantage of the responsiveness of the guest molecule to an external stimulus, leading to a molecular change 4.2.1. pH-Responsive Molecules (e.g., charge, conformation) that release the stimuli-responsive guest molecule from the supramolecular host–guest complex. Molecular components containing acidic or basic groups are sus- Amongst the different type of macrocycles (e.g., cyclodex- ceptible to interact with aqueous media depending on the pH trin (CD),[462] curcubit[n]uril (C[n]B),[463] calix[n]arenes,[464] and of the solution, which in fact is related to their ability to react pillar[n]arenes,[465] see chemical structure in Figure 13A), CDs with hydroxide ions (OH− ) or protons (H+ ), respectively. Thus, are the most utilized ones. Cyclodextrin is commonly composed pH-responsive molecular switches are those that can promote of six, seven or eight glucopyranoside monomers (namely, 𝛼-CD, a readable macroscopic change by alternately modulating the 𝛽-CD, and 𝛾-CD, respectively) forming a truncated cone struc- pH above or below the pKa of the molecular unit. While the ture with an inner hydrophobic cavity and an outer hydrophilic properties of optically active molecules can be tuned by vary- surface.[466] As illustrates in Figure 13B, five main types of guest ing the pH[438–440] (typically yielding to an “on/off” pH sensor), molecules—1) ferrocene as redox-responsive,[467] 2) imidazole other properties, such as hydrophilicity[441] or conductivity,[442] as pH-responsive,[468] 3) azobenzene as light-responsive,[469] 4) can be reverse by changing their charge state. In the latter, bipyridine as ion-responsive,[470] and 5) adamantane as thermal- changes on the charges accumulated at the interface of elec- responsive molecular units[471] —are widely utilized to promote tronic devices carrying pH-responsive molecules can be read reversible supramolecular switches, since only one molecular out via double-layer capacitance by simply changing the pH of state can fit the hydrophobic cavity of cyclodextrin.[472] the electrolyte, fact that will promote the protonation or de- Alternatively, C[n]B is another class of well-studied macrocy- protonation of the sensitive molecular moiety.[241,443] The most cles that allows for hosting more than one guest molecule, mak- employed acidic molecules are those made of carboxylic acids, ing it possible to reach complex systems triggered by more than phosphoric acids, sulfonic acids, or boronic acids.[444] Otherwise, one external stimuli (known as orthogonal systems).[367] For ex- main basic molecules are those containing in their skeleton N- ample, Tian et al. reported the suitability of C[8]B as a single rich groups with nonbonding electron pairs, such as amines,[445] supramolecular entity to simultaneously form host–guest het- pyridines,[446] imidazoles,[447] piperazines,[448] hydrazones,[449] eroternary complexes with both redox-responsive (i.e., methylvi- pyrrolidines,[450] and morpholines.[451] In addition, molecules ologen) and light-responsive (i.e., azobenzene) molecules.[473] Adv. Mater. 2023, 2305546 2305546 (16 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 13. A) Molecular structure of main cone-shaped macrocycles: cyclodextrins, curcubit[n]urils, calix[n]arenes, and pillar[n]arenes. B) Illustration of a reversible host–guest complex inclusion triggered by different external stimuli, highlighting the exemplification of ferrocene, imidazole, azobenzene, bipyridine and adamantane as redox-responsive, pH-responsive, light-responsive, ion-responsive, and thermal-responsive complexes, respectively. 4.3. Spin-Crossover Molecular Switches 5. Stimuli-Responsive i2DMs for Molecule-Programmable Nanoelectronics The spin-crossover phenomenon describes the transition from a low to a high spin state by the help of an exter- The chemistry of molecular electronics for performing binary nal stimulus, leading to the field of spintronics.[474,475] logic functions arose in the late 20th century with the pioneer- Spin-crossover molecules are those molecules presenting ing work published by de Silva in 1993, who demonstrated the two bistable spin states—with different structural, mag- feasibility of analyzing a molecular optical switch in terms of the netic, and/or electronic properties—which can be reversibly Boolean algebra for processing information, analogously to elec- switched upon exposure to external stimuli, whether physi- tronic systems.[487] Since then, the readout of electrical signals cal or chemical.[476,477] In general, spin-crossover molecules between at least two well-defined molecular states (0, 1, also re- are mainly composed of a central transition-metal ion, such ferred to ON/OFF or YES/NO) has been at the heart of the mod- as Fe(II),[478] Fe(III),[479] Co(II),[480] Mn(III)[481] or Ni(II),[482] ern information.[488,489] Due to the surface on any material can be usually coordinated to N-donor ligands.[483] While changes directly interconnected with its surrounding medium, a simple in pressure, light and temperature are the primary phys- change in the charge state or geometry of a molecule can have a ical triggers that induce spin-crossover in organometallic significant impact on the performance of electronic devices. Fur- molecules,[484] chemical inputs encompasses both covalent ther, molecular electronics are not only capable of changing prop- and noncovalent interactions involving metal complexes erties upon demand (programming), but also sensing their envi- with an analyte, complex dissociation, or ligand exchange in ronment (e.g., by employing host supramolecular components solution.[485,486] to tailor host–guest interactions with target molecules driven by Adv. Mater. 2023, 2305546 2305546 (17 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de external inputs). Consequently, the use of molecular moieties as rent levels, opening new avenues toward its implementation as active electronic components offers great prospects not only for multilevel nonvolatile memory. an eco-friendly miniaturization from a simple bottom-up chemi- Su et al. evidenced an innovative mode of molecular switch- cal approach, but also for making them compatibles with biolog- ing, known as stereolectronic switching, which was displayed by ical systems. Particularly, the innovative combination of the out- employing oligosilanes[504] and oligogermanes[505] —considered standing properties of i2DMs—including atomic-level-thickness here as analogous of silanane- and germanane-based Xanes, operation and reduced short-channel effect—[490] with the in- respectively—carrying methilthiomethyl linkers when probed by herent responsiveness of active molecules[491] promises to over- a scanning tunneling microscopy-based break-junction (STM- come the barriers of electronics miniaturization and task-specific BJ) platform. In particular, both molecular systems exhib- applications.[15] ited two different conductance states (low G state and high Although several pristine i2DMs have been applied to directly G state), which were reversibly switched from a lower to or indirectly perform some logical functions,[492–500] the imple- higher conductance by elongating or compressing the molec- mentation of stimuli-responsive i2DMs for electrically monitor- ular junction by few angstroms. This singular way of switch- ing bistable molecular switches is still in a baby stage, which ing was ascribed to the strongly coupled Si─Si and Ge─Ge 𝜎- might provide new avenues toward the development of a new bonds that couple the stereolectronic features of the sulfur– family of molecule-programmable nanoelectronics to advance methylene 𝜎-bonds of the two terminal linker groups of the in this conceptual crossover between materials chemistry and molecule.[506] computation. What follows summarizes the recent advances of stimuli-responsive i2DMs to advance in the current post- Moore era, pointing out the monitoring of different molecular 5.1.2. Stimuli-Responsive TMCs changes—triggered by an external stimulus of any nature—as an electrical output signal (e.g., electrochemical or electronic). Several works reported by the research group of Samori have It is worth to note that the integration of active molecules on demonstrated the suitability of employing stimuli-responsive electronic devices is not necessary realized to optimize charge TMCs as active 2D channel materials for the fabrication of high- transport, but rather to control it by implanting new properties to performance FETs, promoting a reversible optical control over the material/device, enabling the performing of multifunctional the output current as a result of a molecular change.[503,507–509] tasks otherwise inaccessible for the pristine counterparts.[501] Briefly, in order to achieve efficient FET devices for performing binary logic operations, high charge-carrier mobilities, high on- state/off-state conductance ratios, high conductivity, and low off- 5.1. Electrically Monitoring Bistable Molecular Switches state conductance are desirable.[510] To reach some of these goals, different TMDs, including MoS2 and WSe2 , have been consid- In the last two decades, molecular switching has established it- ered for their functionalization with photoresponsive molecules, self as a pivotal approach for the development of a wide range such as azobenzene,[508] spiropyran,[509] and diarylethene[503,507] of responsive materials and surfaces.[502] Molecular switches can derivatives. In general, the resulting light-responsive TMD-based be described as single input–single output devices exhibiting re- FETs provided two distinguishable photoswitchable charge trap- versible states triggered by an external stimulus (input), whose ping levels (electrons and/or holes) by alternating the light source electrical dependence with regarding the molecular state can be with UV and visible light irradiation. utilized to electrically store information (output) in form of digital For example, the work carried out by Gobbi et al. revealed signals (i.e., zeros (0) and ones (1) in the binary code). Herein, the how the immobilization of spiropyran upon two different 2D chemistry behind the following examples is based on reversible materials (i.e., graphene, MoS2 ) generate atomically precise su- chemical reactions triggered by external stimuli (e.g., isomeriza- perlattices, whose integration in FET devices provides a precise tion, protonation/deprotonation, cyclization, complex formation, control over local charge carrier density derived from a light- redox reactions, or spin-crossover), where the different molecu- triggered structural reorganization (see Figure 14A).[511] In addi- lar states have a significant impact on the i2DMs electrical per- tion, same author successfully interfaced different diarylethene formance. derivatives on both WSe2 - and black phosphorous-based FETs, demonstrating the unipolar modulation of either electron trans- port or hole transport, respectively.[503] The photoinduced iso- 5.1.1. Stimuli-Responsive Xenes merization of diarylethene derivatives (open/closed forms) pro- moted different energy levels, resulting in a bistable molecular Regarding to the use of stimuli-responsive Xenes for electri- switch electrically monitored by means of charge transport. Al- cally reading molecular switches, Qiu et al. engineered a black ternatively, the suitability of fully exploiting ambipolar switching phosphorous-based field-effect transistor (FET) functionalized of charge transport in WSe2 has been recently demonstrated via with a diarylethene derivative to optically modulate the hole trans- dual functionalization with two different photocromic molecules port of FET devices.[503] The different electrical states achieved (n- and p-type diarylethene derivatives), each with specific energy derives from the different doping effect resulting from the ring- levels engineered to selectively trap either electrons or holes from open/ring-closing of the bistable molecular photoisomers, fact WSe2 .[507] Interestingly, an optically switchable multilevel WSe2 - that directly affects to the hole trapping process of the i2DM. based FET with ability to simultaneously modulate both electron Further, the photoresponsive black phosphorous-based FET sys- and hole transport through remote light stimuli was achieved tem displayed excellent data-retention capacity at different cur- (Figure 14B). Adv. Mater. 2023, 2305546 2305546 (18 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 14. Electrically reading molecular photoswitches using stimuli-responsive i2DMs. A) Photoresponsive MoS2 -based FET device employing a spiropyran molecular derivative, showing how the light-driven isomerization favors a structural rearrangement. a1 ,a2 ) The scanning tunneling micro- scopic images of the molecular assemblies obtained before and after UV irradiation, respectively (note: images were obtained with alternative 2D materi- als like graphene). a3 ) IDS –VGS performance of the photoresponsive MoS2 -based FET device after several cycles of UV–vis light irradiation, demonstrating the reversibility of the molecular switch. Adapted with permission.[511] Copyright 2018, Nature. B) Energy level diagram of energy transport between WSe2 and the engineered photoresponsive diarylethene (DAE) derivatives, as both open (o) and closed (c) isomers. b1 ) Molecular and device structure of the i2DM-based FET. b2 ) Electrical performance of WSe2 /DAE blend FET device showing the bistable molecular photoswitch by means of drain current (Ids ) modulation over 10 illumination cycles with alternative UV (red shaded areas) and visible (blue shaded areas) light. Adapted with permission.[507] Copyright 2018, Wiley. Beyond photoresponsive molecules, alternative stimuli- molecular switch. Two distinct doping effects derived from its responsive molecular components have also been explored to neutral or charged state were achieved, fact that efficiently tuned modulate the electronic properties of TMD-based devices. Zhao the electron density in MoS2 (Figure 15A). Sideri et al. recently et al. functionalized MoS2 with a redox-responsive molecule as functionalized 1T-MoS2 (the metallic phase counterpart this ferrocene.[512] After immobilizing the thiol-rich ferrocene on TMD) with a Hamilton-type host molecule (i.e., a barbiturate MoS2 via vacancy engineering, the resulting stimuli-responsive derivative) to explore supramolecular host–guest interactions was integrated in an FET to electrically read out a bistable with a redox-active ferrocene-barbiturate guest via H-bond Adv. Mater. 2023, 2305546 2305546 (19 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 15. Examples of redox- and thermal-responsive i2DMs exhibiting two electrical states. A) Schematic illustration of back-gate monolayer MoS2 - based FET and its functionalization with a thiol-rich ferrocene to electrically read out a redox-triggered molecular switch. a1 ) Back-gate transfer charac- teristics of the redox-responsive MoS2 -based FET with regarding to the electrochemical state of ferrocene (oxidized/reduced) in the linear scale regime. Adapted with permission.[512] Copyright 2020, Springer. B) Synthetic approach for the fabrication of stimuli-responsive MoS2 with dual spin-crossover modulation (temperature and light). b1 ) Electrical performance of the bistable molecular switch triggered by temperature. Inset: TEM image of the switchable molecular-based spin-crossover MoS2 . Adapted with permission.[514] Copyright 2021, Nature. formation.[513] The formation of the supramolecular complex This work represents an excellent example of how a molecular leads to an electrochemical response derived from the presence moiety can serve to tune the strain applied on i2DMs and of the redox-active guest molecule. Although this work does therefore, its electronic structure and electric conductivity. not directly present a molecular switch, the authors believe on the possibility of switching this material in the future by taking advantage of the temperature or solvent-dependent formation 5.1.3. Stimuli-Responsive MXenes of that hydrogen bonds, which would make possible to achieve to distinguish electrochemical states. Torres-Canavillas et al. Moving to stimuli-responsive MXenes, Muñoz et al. reported the novelty engineered a switchable molecular-based spin-crossover covalently anchoring of both a light-responsive molecule (i.e., MoS2 material triggered by two different stimuli (light and tem- azobenzene) and a pH-responsive molecule (i.e., tryptophan) perature inputs), which serves to generate strain over the MoS2 upon Ti3 C2 Tx –MXene through esterification chemistry for elec- layer that promotes substantial and reversible changes in the trochemically monitoring bistable molecular switches on the top electrical and optical properties of the i2DM.[514] For this goal, of a carbon-based electrode. On the one hand, the photo-driven MoS2 was functionalized with 3-iodopropyl(trimethoxysilane) inputs to isomerize the azobenzene molecule from the E-form to (IPTS, as molecular moiety) followed by [Fe(Htrz)2 (trz)](BF4 ) co- the Z-form resulted in two distinguished electrical states at the ordination polymer covered with a silica shell as spin-crossover responsive i2DM/electrolyte interface that were successfully dis- unit, being Htrz: 1,2,4-triazole and trz: triazolate (Figure 15B). cerned via cyclic voltammetry.[217] Remarkably, a dual modulation Adv. Mater. 2023, 2305546 2305546 (20 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 16. Reading molecular switches using responsive MXenes with electrochemical readout. A) Photoresponsive Ti3 C2 Tx -based electrode employing an azobenzene molecular derivative. a1 ) Cyclic voltammograms at the two different electrochemical states (before and after irradiation with UV light), with a2 ) its corresponding molecular switchability after several cycles of UV/vis light irradiation. Adapted with permission.[217] Copyright 2022, Royal Society of Chemistry. B) pH-responsive Ti3 C2 Tx -based electrode employing tryptophan as active molecule, whose molecular switch resulted from the protonation/deprotonation of the amino group by modulating the pH of the electrolyte (before and after the pKa ). b1 ) Real part contribution capacitance acquired at the two different pHs. Inset: control experiment using the pristine Ti3 C2 Tx –MXene). b1 ) Reversibility of the system by modulating the pH for several cycles. Adapted with permission.[241] Copyright 2021, American Chemical Society. of the electrochemical output signals was obtained by means of triggered transition from hydrophilic to hydrophobic promotes current intensity peak (Ip ) and peak to peak separation (ΔE) by us- significant changes on the electrochemical performance, yielding ing a redox marker (i.e., [Fe(CN)6 ]3−/4− ) as the electrolyte. Those to 90% capacitance suppression when exposed to high tempera- electrochemical changes were ascribed to the molecular isomer- tures. Sun et al. interfaced a stimuli-responsive polymeric moi- ization from the straight E-form of azobenzene to the Z-form ety (PNIPAM) on MXene to prepare a hydrogel that response to counterpart after UV light irradiation, fact that hinders the acces- two different inputs (i.e., light and force), resulting in two dif- sibility of the redox marker to the electrode surface, and therefore ferent outputs (i.e., thermal and electrical, respectively).[516] Be- lower Ip and higher ΔE values were yielded (Figure 16A). On the yond the outstanding photothermal properties exhibited under other hand, a multiresponsive Ti3 C2 Tx –MXene was synthesized NIR irradiation, the stimuli-responsive MXene-based hydrogel by immobilizing an ammino acid as tryptophan, in which its pH- also presents significant changes on conductivity by means of re- responsive properties were exploited to reach a bistable molecu- sistance when exposed to diverse deformation inputs (e.g., bend- lar switch once the Responsive MXene was immobilized on the ing, elongation, and compression), demonstrating excellent cy- electrode surface.[241] In this case, the protonation/deprotonation cling stability and durability (Figure 17A). of the amino group—induced by modulating the pH of the solu- tion (lower and higher than the pKa of the NH2 /NH3 + group)— was monitored by means of real capacitance values (Cre ), since 5.1.4. Stimuli-Responsive TMOs/TMHs this parameter is directly related to the density of charges accu- mulated at the electrode/electrolyte interface (Figure 16B). Although the molecular functionalization of TMHs exhibiting In addition, MXene-based i2DMs have also been interfaced di- switchability has been widely explored through the monitor- rectly or indirectly with stimuli-responsive polymeric moieties ing of optical outputs,[517,518] the electrical readout of molecular to electrically modulate electrical properties. On the one hand, switches is almost an unexplored field. To date, only a stimuli- Yu et al. prepared a MXene-based supercapacitor loaded with a responsive TMH based on a thermal input–electrochemical out- thermal-responsive electrolyte (i.e., poly(N-isopropylacrylamide- put system has been reported. Concretely, Dou et al. function- co-gly-cidylmethacrylate), PNGM) to meet the challenge of work- alized a CoAl-based layered double hydroxide material with a ing at high temperatures.[515] While at room temperature the temperature-triggered polymer (i.e., PNIPAM) through a layer- ions of the electrolyte can migrate freely due to the hydrophilic by-layer assembly technique upon the surface of an iron thin ox- nature of PNGM, at high temperatures the electrolyte forms ide electrode, and the reversibility of the thermal-stimuli system a hydrophobic network that hinders ion migration. This heat- was electrochemically revealed using both cyclic voltammetry Adv. Mater. 2023, 2305546 2305546 (21 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de Figure 17. Stimuli-responsive i2DMs carrying an active polymeric component (i.e., PNIPAM) exhibiting two different electronic states. A) Schematic illustration for the preparation of a force-responsive MXene-based hydrogel. Electrical performance of the stimuli-responsive MXene: a1 ) real-time detection of human motions (finger bending and recovering) with a2 ) its corresponding cyclability in 10 loading–unloading cycles. a3 ) Relative resistance changes in response to compressive strain of 20%, 40%, and 60% with a4 ) its corresponding cyclability in 10 compressing–recovering cycles. Adapted with permission.[516] Copyright 2021, Wiley. B) Schematization of the synthetic approach carried out to realize an electronic device based on a thermal- responsive TMH for electrically monitoring a molecular switch. b1 ) Intensity signals achieved at different temperatures. Inset: device switchability at two different temperatures (20 and 40 °C). Adapted with permission.[519] Copyright 2012, American Chemical Society. and electrochemical impedance spectroscopy tools.[519] By mod- functionalization strategies to make 2D materials functional for ulating the temperature between 20 and 40 °C, two electronic task-specific applications on-demand. Concretely, i2DMs, have states were observed by taking advantage of the contraction– been identified as promising candidates to lead this post-Moore expansion configuration of PNIPAM, resulting in low–high im- era thanks to their outstanding and diverse physicochemical char- pedimetric values, respectively (Figure 17B). In addition, the sen- acteristics, as well as large surface-to-volume ratio that make sibility of the electrochemical system toward the oxidation of them highly sensitive to changes in the surrounding environ- glucose at the two different thermal states was also considered, ment. Although very promising from a scientific point of view, demonstrating better results at 40 °C due to the better electro- the reality is that the field of i2DMs is still in an early stage, and chemical behavior observed. therefore further research must be focused on understanding the chemical reactivity of pristine i2DMs in order to introduce novel 6. Conclusions and Outlook functionalities in a controllable manner by tailoring interactions between i2DMs and the moiety of interest. The synthesis and exploration of alternative 2D materials (e.g., In the last decade, molecular engineering has arisen as a i2DMs), beyond graphene, has opened up new avenues toward powerful approach to fine-tune the physicochemical properties the industrial implementation of unconventional 2D materials- of 2D materials, making it possible to fulfill the central chal- based nanoelectronics to be at the forefront of this emerging lenge of materials science by implanting a la cartè novel molec- technological era known as post-Moore. 2D materials are named ular features. Thus, molecular engineering has given light to to address the current digital transition challenges of further integrate the functional programmability of molecular science miniaturization, resulting in more energy-efficient nanoelectron- into the next generation of nanoelectronics for digital processing ics displaying faster memory, computing, biosensing, and actu- and communication. In particular, by covalently anchoring active ating capabilities. However, the large variety of 2D materials with molecular components, novel and robust active/functional mate- their respective inherent characteristics and specific chemical re- rials and devices (i.e., stimuli-responsive i2DMs) can be realized. activity clearly demand for general, robust, and straightforward Stimuli-responsive i2DMs can be seen as “intelligent” materials Adv. Mater. 2023, 2305546 2305546 (22 of 31) © 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH 15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202305546 by Readcube (Labtiva Inc.), Wiley Online Library on [18/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License www.advancedsciencenews.com www.advmat.de in which a controlled molecular transformation (e.g., conforma- plore optical approaches. Finally, the current molecular func- tion, charge state, etc.) triggered by an external input can be suc- tionalization of i2DMs has been mainly restricted to photore- cessfully transduced into electrical output signals, promoting the sponsive molecules by taking advantage of their dopant effect acquisition of programmable characteristics capable of perform- and therefore, other on-demand capabilities must be explored via ing binary logic operations at the molecular level. This perfor- anchoring alternative stimuli-responsive molecular components. mance is analogue to the one displayed by conventional Si-based Indeed, the covalent molecular immobilization of ad hoc active semiconductor technology. components on i2DMs can provide a rational control over the Herein, the molecular functionalization of pivotal i2DMs nanoscale assembly of molecular switches, fact that can facilitate (e.g., Xenes, TMCs, MXenes, TMOs, and TMHs) has been in- the better understanding of the mechanisms behind such macro- depth summarized, with main focus on covalently engineer- scopic effects. ing stimuli-responsive i2DMs for the development of molecule- Overall, the covalent functionalization of i2DMs with molecu- programmable nanoelectronics. Concretely, the assembly of ac- lar components displays promising application potential in sev- tive molecular moieties exhibiting bistable molecular switches eral fields and provides a powerful platform for electrically mon- at interfaces is particularly appealing, since the behavior of itoring bistable molecular switches. However, the implementa- the resulting stimuli-responsive i2DMs can be simply manipu- tion of stimuli-responsive i2DMs presents some challenges, in- lated by any type of external input (e.g., optical, electrical, pH, cluding i) precise control over the external input, especially in real supramolecular, etc.) to address binary logic functions. In addi- environments, ii) long-term stability (durability), iii) costly large- tion, from an operational point of view, electrical outputs consti- scale production (scalability), and iv) versatility for different ap- tute a convenient way to read out the state of the system. Con- plications. To solve the aforementioned challenges, key solutions sequently, research in combining i2DMs with molecular engi- should be focused on i) developing at-point-of-use systems for neering will not only produce fundamental new knowledge, but real-time monitoring of molecular switches, ii) implementing co- also will play a key role in the development of the next gen- valent molecular functionalization methods to synthesize robust eration of molecule-programmable nanoelectronics (e.g., mem- heterostructures in order to prevent leakage of molecular com- ories, spintronics, logic gates, biosensors) for logical operation ponent, iii) improving manufacturing techniques like 3D print- processing to be implemented in the near future. Interestingly, ing by designing inks and filaments based on stimuli-responsive the implementation of stimuli-responsive i2DMs to read out elec- i2DMs, and iv) utilization of more than one molecular compo- trical outputs has been highlighted with prominent examples of nent to obtain multi-responsive i2DMs to enrich binary logic op- signal processing, demonstrating the suitability of transferring erations (e.g., orthogonal switches). Consequently, only the time the characteristics of active molecules to i2DM-based nanoelec- will tell us whether these promising stimuli-responsive i2DMs tronics to speak the complex language of information technol- will lead to the manufacturing of a new generation of digital de- ogy. However, the practical integration and application of stimuli- vices for information processing. responsive i2DMs as unconventional post-Moore technology for future nanoelectronics will depend on investing efforts on funda- mental studies on various aspects of this research area, such as Acknowledgements efficient molecular functionalization approaches to retain their J.M. is indebted to the Ramón y Cajal Program (RYC2021-033820-I Fellow- signal transduction abilities. ship) funded by MCIN/AEI/10.13039/501100011033 and by the European Amongst the different families of i2DMs summarized in this Union “NextGenerationEU/PRTR”. Review, TMCs in general, and MoS2 in particular, are by far the most explored ones for electrically reading molecular switches. This fact might be mainly ascribed to their commercial availabil- Conflict of Interest ity, low-cost production, inherent semiconductor nature, chemi- cal stability, as well as versatility for covalently anchoring molec- The author declares no conflict of interest. ular components. Alternatively, black phosphorous has demon- strated to be the most explored member of Xenes’ family thanks to its tunable bandgap and high carrier mobility. In this line, the Keywords promising achievements obtained by black phosphorous are pro- functionalization, molecular electronics, molecular switches, MXene, moting the active investigation of additional Xenes/Xanes, like transition-metal dichalcogenide gemanene/germanane and silicene/silicane. Although the fam- ily of MXenes is currently experiencing a boom in the field of Received: June 9, 2023 electronics owing to their excellent electrical conductivity and Revised: October 10, 2023 suitability to be interfaced with molecular components, the te- Published online: dious and often harmful synthetic methodologies commonly used for synthesizing MXens from MAX phases today consti- tute a fundamental obstacle that hinders the real implementa- [1] G. E. Moore, IEEE J. Solid-State Circuits 2009, 11, 33. tion of MXenes. Regarding to TMOs and TMHs, their versatility [2] Y. Y. Illarionov, T. Knobloch, M. Jech, M. Lanza, D. Akinwande, M. and tunable properties, in combination with their range of elec- I. Vexler, T. Mueller, M. C. Lemme, G. Fiori, F. Schwierz, T. Grasser, trical properties—from semiconductor to metal—make them at- Nat. Commun. 2020, 11, 3385. tractive for a wide range of electronic applications; nonetheless, [3] M. Forshaw, R. Stadler, D. Crawley, K. 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