pubs.acs.org/cm Article Water-Stable Carborane-Based Eu3+/Tb3+ Metal−Organic Frameworks for Tunable Time-Dependent Emission Color and Their Application in Anticounterfeiting Bar-Coding Zhen Li, Rosario Núñez, Mark E. Light, Eliseo Ruiz, Francesc Teixidor, Clara Viñas, Daniel Ruiz-Molina, Claudio Roscini,* and José Giner Planas* Cite This: Chem. Mater. 2022, 34, 4795−4808 Read Online See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. ACCESS Metrics & More Article Recommendations * sı Supporting Information ABSTRACT: Luminescent lanthanide metal−organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though Downloaded via 158.109.48.66 on May 10, 2023 at 10:27:58 (UTC). their implementation still remains a challenge. To be suitable for practical applications, Ln- MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of mCB-EuyTb1−y (y = 0−1) MOFs using a highly hydrophobic ligand mCBL1: 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo- dodecaborane. The new materials are stable in water and at high temperature. Tunable emission from green to red, energy transfer (ET) from Tb3+ to Eu3+, and time-dependent emission of the series of mixed-metal mCB-EuyTb1−y MOFs are reported. An outstanding increase in the quantum yield (QY) of 239% of mCB-Eu (20.5%) in the mixed mCB- Eu0.1Tb0.9 (69.2%) is achieved, along with an increased and tunable lifetime luminescence (from about 0.5 to 10 000 μs), all of these promoted by a highly effective ET process. The observed time-dependent emission (and color), in addition to the high QY, provides a simple method for designing high-security anticounterfeiting materials. We report a convenient method to prepare mixed-metal Eu/ Tb coordination polymers (CPs) that are printable from water inks for potential applications, among which anticounterfeiting and bar-coding have been selected as a proof-of-concept. ■ INTRODUCTION Porous coordination polymers (CPs), also known as metal− diplomas, and certificates,23−27 which require an ever- increasing tunability (e.g., emission colors) and authentication organic frameworks (MOFs), are a class of highly crystalline complexity. However, regardless of the great potential of these materials formed by metal ions or metal clusters connected by materials, to date they have proved unsuitable for practical multitopic organic linkers, which have attracted extensive applications due to their limited chemical28−35 and/or attention over the past few decades.1−4 Their large surface optical27,36 stability under environmental conditions (e.g., areas, framework flexibility, and tunable pore surface proper- humidity, temperature, etc.). ties, as well as “tailor-made” framework functionalities, Herein, we hypothesized that such limitations can be empower them to be promising candidates for a diverse overcome with the introduction of carborane clusters such as range of applications.2,5−13 Especially interesting is the icosahedral carboranes 1,n-C2B10H12 (n = 2, 7 or 12), a class of combination of MOFs with lanthanide (Ln) ions resulting in commercially available and exceptionally stable three-dimen- inherent optical properties, including high luminescence sional (3D) aromatic boron-rich clusters that possess material- quantum yields, narrow and strong emission bands, large favorable properties such as thermal/chemical stability and Stokes shifts, long luminescence lifetimes, and an emission high hydrophobicity.37−43 Carborane-based MOFs were first wavelength undisturbed by the surrounding chemical environ- synthesized at Northwestern University, and they showed an ment.14,15 Their luminescence is associated with an energy increase in their thermal stabilities among other interesting transfer (ET) from the ligand, acting as an antenna, owing to properties.44−51 The spherical nature of the carboranes, with its larger extinction coefficient, to the accepting electronic levels of the emitting lanthanides and it is potentially interesting in a variety of applications, such as e.g., sensors, Received: January 31, 2022 optoelectronic and in solid-state lighting (SSL) devices, or Revised: April 19, 2022 bioimaging among others.16−22 Of particular interest would be Published: April 29, 2022 the exploitation of emissive Ln-MOFs as optical markers for high-security anticounterfeiting technologies aimed to prevent illegal copies of sensitive identity documents, banknotes, © 2022 The Authors. Published by American Chemical Society https://doi.org/10.1021/acs.chemmater.2c00323 4795 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article Figure 1. Crystal structure of mCB-Tb. (a) View of the coordination of mCBL1 to the three independent Tb atoms that are repeated along the structure to provide one-dimensional (1D) inorganic rod-shaped chains and (b, c) two perpendicular views of the extended 3D framework along the b and a axes, respectively. Green polyhedra represent the Tb coordination spheres and H atoms are omitted for clarity. Color code: B, pink; C, gray; O, red; N, dark blue; and Tb, green. slightly polarized hydrogen atoms and the presence of the {[(Ln)3(mCBL1)4(NO3)(DMF)n]·Solv} (mCB-Ln, where hydride-like hydrogens at the B−H vertexes, make the Ln = Eu, Tb, or EuxTb1−x; Figure 1). In addition to their carboranes very hydrophobic. Thus, we have recently explored high thermal and water stabilities, the preparation of mixed and demonstrated the possibility of increasing the hydrolytic mCB-EuxTb1−x-doped MOFs allowed for fine control and high stability of CPs or MOFs by incorporating hydrophobic tunability of both steady-state and time-dependent emission carborane-based linkers52−57 into these porous materials.58−63 color (from green to red) and lifetime luminescence (from Our strategy has provided the most water-stable Cu-paddle about 0.5 to 10 000 μs). An outstanding increase of 237% of wheel MOF in the literature, which is related to the high luminescence quantum yield from the single-ion mCB-Eu hydrophobicity of the m-carborane ligand mCBL1: 1,7-di(4- MOF (20.5%) to the mixed mCB-Eu0.1Tb0.9 MOF (69.2%) is carboxyphenyl)-1,7-dicarba-closo-dodecaborane (Figure 1).61 achieved, owing to a highly effective ET process from Tb3+ to Beyond stability, the delocalized electron density is not Eu3+. Furthermore, the time-dependent luminescence of mixed uniform through the cage, giving rise to extraordinary MOFs and the typical discrete visible emission bands of Eu differences in the electronic effects of the cluster.64 This and Tb ions allowed for time-dependent bar-coding, whose unusual electronic structure is often highlighted by considering code evolution in the ms scale can easily be tuned by carboranes as inorganic three-dimensional “aromatic” ana- controlling the Eu/Tb ratio. These advanced optical proper- logues of arenes.65 In this regard, for the last 25 years, a ties, combined with the demonstrated printability through remarkable influence of icosahedral carboranes on the spray-coating, make these materials very promising as invisible photophysical properties of organic fluorophores66−78 or in security inks for future anticounterfeiting technologies. their transition metal compounds has been reported.57,79−81 However, as far as we know, there are no reports on luminescence properties of carborane-based MOFs82 and ■ RESULTS AND DISCUSSION Syntheses, Characterization, and Optical Stability of therefore the antenna effect has not yet been reported for a Single-Ion Carborane-Based mCB-Ln. Colorless crystals of carborane linker. [(Eu) 3 (mCBL1) 4 (NO 3 )(DMF) x ] n ·solv (mCB-Eu) and As a proof-of-concept, in this work, we report the [(Tb)3(mCBL1)4(NO3)(DMF)x]n·solv (mCB-Tb) were ob- preparation and full characterization of a series of isostructural tained in high yields by solvothermal reactions in a mixture of water-stable m-carborane Ln-MOFs, N,N-dimethylformamide (DMF)/methanol/H2O at 95 °C for 4796 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article 48 h (see the Experimental Section for details and Figure S1, (Figure S7, Supporting Information). The absorption spectra Supporting Information). Single-crystal X-ray diffraction of mCB-Ln display slight broadening of the UV bands. Upon revealed that mCB-Tb crystallizes in the monoclinic Pn continuous-wave irradiation at λex = 280 nm in an air space group, and the analysis of the structure revealed the atmosphere and at room temperature, both mCB-Eu and formation of a 3D framework based on the novel mCB-Tb solid crystals showed intense luminescence in the [(Tb)3(COO) 8(NO 3)(ODMF) 4] secondary building unit visible region and sharp and well-resolved emission bands (SBU) (Figure 1 and Table S1, Supporting Information). (Figure 2). The crystals’ emissions were also observable by the The new SBU is composed of three nonequivalent crystallographic terbium atoms, which are connected and capped by bridging, chelate bridging or chelate mCBL1, chelate NO3−, and DMF molecules. Whereas, Tb(1) and Tb(3) atoms (Figure 1) are eight-coordinated and Tb(2) is seven-coordinated. As shown in Figure 1, six mCBL1 ligands are coordinated to Tb(1) and those adopt two different coordination modes (bridging and chelate bridging). The coordination of Tb(1) is completed by a DMF molecule. Tb(2) (Figure 1) shows, however, two coordinated DMF molecules and five mCBL1 ligands, all with bridging coordination. Tb(3) shows a DMF molecule, a chelate NO3−, and five mCBL1 ligands, the latter adopting bridging coordination with the neighboring Ln atoms. Such coordina- tion provides 1D-chains of Tb atoms, which are connected by the mCBL1 ligands and thus provide the observed 3D structure (Figure 1). The varied coordination around the three crystallographic-independent Ln atoms results in three different Tb−Tb metal distances (Tb(1)−Tb(2) 5.5830(8), Tb(2)−Tb(3) 5.2550(7), and Tb(1)−Tb(3) 4.6398(7) Å). The Tb−O bond distances are in the range of 2.272(10)− 2.906(10) Å, all of which are comparable to related compounds.83−86 Fourier transform infrared (FTIR) spectroscopy (Figure S2, Supporting Information) and powder X-ray diffraction (PXRD; Figure S3, Supporting Information) analysis for mCB-Eu and mCB-Tb compounds revealed that both are isostructural and their experimental patterns match very well with those simulated from the X-ray structure of mCB-Tb, therefore, suggesting that the as-synthesized materials are pure phases. Thermogravimetric (TGA; Figure S4, Supporting Figure 2. Solid-state emission spectra of mCB-Eu (a) and mCB-Tb Information) and elemental analyses confirmed the chemical (b) under continuous-wave irradiation (λex = 280 nm) at room composition of mCB-Eu and mCB-Tb. TGA curves for these temperature. Insets: optical microscopy images of the corresponding two materials revealed good thermal stabilities as the crystals (λexc = 280 nm). (c) Photograph of the hand-painted logo of frameworks are stable up to 400 °C. the Institut de Ciència de Materials de Barcelona (ICMAB) with As expected, both mCB-Eu and mCB-Tb showed very high mCB-Eu and mCB-Tb crystals (λex = 254 nm). stability in neutral water and aqueous solutions of a broad range of pH values (3−11) for at least 5 days. PXRD traces of naked eye, as shown in the insets of Figure 2a,b. The both, before and after incubation in water in a closed vial luminescence spectrum of mCB-Eu presented the typical perfectly match the simulated pattern derived from the single- emission feature of Eu-based materials, with peaks at 591, 614, crystal structure of mCB-Tb (Figure S5, Supporting 650, and 699 nm, which correspond to characteristic Information). In addition, optical images of the crystalline transitions of the Eu3+ ion: 5D0 → 7FJ (J = 1, 2, 3, and 4),87 samples after their immersion in water under the above- respectively, with the strongest being the 5D0 → 7F2 transition mentioned conditions showed no significant morphology at 614 nm (Figure 2). Overall, the mCB-Eu crystal yielded a change in the needle-like crystals nor evidence of surface strong orange luminescence quantum yield (Φ = 20.5%), with cracking (Figure S5, Supporting Information). Such high a 1931 CIE color coordinate (0.62, 0.38). mCB-Tb showed stability is ascribed to the presence of the carborane ligand. the typical luminescence of the Tb3+ ion, with emission peaks The optical properties of the carborane-based mCBL1 ligand at 489, 543, 582, and 621 nm, which are assigned to the 5D4 → and the corresponding Eu3+ and Tb3+ compounds mCB-Ln 7 FJ (J = 6, 5, 4, and 3)87 transitions of Tb3+ ions. The strongest were investigated by collecting the ultraviolet−visible (UV− emission peak at 543 nm is associated with the 5D4 → 7F5 vis) absorption and emission spectra of the compounds in the transition (Figure 2). mCB-Tb presented a quite efficient solid state. The free ligand mCBL1 exhibits a broad absorption green emission (Φ = 49.8%) with the CIE color coordinate band around λmax ∼ 289 nm attributed to π → π* transitions (0.32, 0.58). These results clearly indicate that the carborane- (Figure S6, Supporting Information). The luminescence based mCBL1 ligand is an excellent light-absorbing antenna spectrum for mCBL1 shows a strong emission at λem = 312 chromophore for sensitizing both ions (vide infra), and the nm (λex = 280 nm) and an overall quantum yield (Φ) of 0.3% resulting MOFs presented quite high solid-state luminescence, 4797 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article which is comparable to other Ln-MOFs (ΦEu‑MOFs = 25−95; S6, Supporting Information). The analysis of the orbitals ΦTb‑MOFs = 7−75).88−90 More importantly, the optical confirms that such transitions are mainly π−π transitions with properties of mCB-Eu and mCB-Tb crystals did not suffer a large contribution from the phenyl rings. Both the calculated significant changes when these materials were suspended in energies of the S1 and T1 states for mCBL1 are significantly water for 5 days or heated up to 180 °C for 24 h (Figure S8, larger than those for some commonly used carbon-based Supporting Information), proving the high stability provided chromophores.14 Thus, to understand the possible role of the by the carborane ligand to the MOF optical properties. In fact, carborane moiety in such unusually high energies of the first water suspensions of the mCB-Eu and mCB-Tb crystals could singlet excitation and triplet for our ligand, we have also be successfully used to prepare two-colored patterned explored the photophysical properties of the related ligand by luminescence drawings (of ICMAB logo) through their substituting the carborane moiety with a phenyl ring deposition onto cellulose papers (Figure 2c and the ([1,1′:3′,1″-terphenyl]-4,4″-dicarboxylic acid, mTDCA) by Experimental Section), which did not affect the emission TDDFT (Figures S11 and S12, Supporting Information). properties. Scanning electron microscopy (SEM) images Consistent with the previous reports,14 both the calculated corroborate the entrapment of microsize crystals between the energies of the S1 and T1 states for mTDCA are significantly fibers of the cellulose papers (Figure S9, Supporting smaller than that for mCBL1. The comparison between the Information), and steady-state luminescence spectra demon- two ligands (Figures S11 and S12, Supporting Information) strate that the crystals preserve their optical properties (Figure shows that the main difference is a symmetry breaking of the S10). empty orbitals, probably due to the smaller symmetry of the To analyze the mechanism of the luminescence process, the mCBL1 ligand for the central carborane. Whereas the mCBL1 photochemical properties of the mCBL1 have been explored ligand structure remains almost unchanged in the S1 and T1 using time-dependent density functional theory (TDDFT) states, that for the mTDCA ligand shows that the noncoplanar methods (see the Computational Details section). It is known ground-state structure results in a two-ring coplanar for the that the antenna effect of the ligand for sensitization of the first triplet state (Figure S12, Supporting Information). This luminescence of lanthanide compounds is due to the transfer difference between the two ligands is reflected in the emission from a triplet state of the ligand to the first excited state of the energies of the triplet (mCBL1, 20449 cm−1; mTDCA, 16 474 lanthanide cataion .14,16 Among others, the efficiency of the cm−1). The orbitals involved in the emission are basically the lowest unoccupied molecular orbital (LUMO) and the highest ligand as a sensitizer is related to the energy of its triplet state. occupied molecular orbital (HOMO) with a larger degree the The energy of the 5D4 and 5D0 first excited states for Tb3+ and localization in one part of the molecule in comparison with the Eu3+ cations for the studied system are 541 nm (18 464 cm−1) singlet due to the decrease of symmetry (Figure 3). The and 614 nm (15 286 cm−1). To have an efficient energy unusually high energy for the triplet state for mCBL1, transfer from the sensitizer ligand to the lanthanide, previous therefore, favored an effective energy transfer through studies14 have estimated that the energy of the triplet of the nonradiated excited states of the metal until it reached the ligand should be at least 1850 cm−1 above the lowest emitting emissive levels and the metal-centered emission took place.14 excited states of the lanthanide. The first triplet state structure Such energy transfer would be much less efficient in the case of of the ligand has been optimized at the TDDFT level and the mTDCA ligand, which has no carborane, as the energy for resulted in a value of 20 449 cm−1 for mCBL1, which perfectly its triplet state is of the order of that for Eu3+ and lower than fits with the requirement for an efficient energy transfer to both that for Tb3+ (Figure S13, Supporting Information). Tb3+ and Eu3+. The involved energies in the first singlet Synthesis, Characterization, and Optical Properties excitation and the triplet energy of mCBL1 are represented in of Mixed-Ion Carborane-Based mCB-EuyTb1−y. Currently, Figure 3 together with the involved orbitals. The first allowed doping diverse Ln3+ ions into the same MOF has become an excitation energies (calculated TDDFT values of 260 nm for emerging method to accomplish stoichiometry-dependent the mCBL1 ligand) are in agreement with those determined in color tunability.16,90,91 Due to the similar coordination the mCBL1 ligand in a solid state around 251−289 nm (Figure environments, various Ln3+ ions can be introduced into the same MOF structure simultaneously. Energy transfer (ET) from one lanthanide to another lanthanide ion has also been observed to enhance the luminescence intensity in mixed- metal Ln-MOFs.88,91−96 For example, it has been reported that such ET between Tb and Eu ions induced up to 70% emission enhancement for the Tb-sensitized Eu emission in Ln-MOFs.88 Thus, after once demonstrating the feasibility of using the hydrophobic carborane ligand to obtain water-stable MOFs with a high luminescence quantum yield, we aimed to investigate the possibility of obtaining other mixed Ln-MOFs (mCB-EuyTb1−y) with variable amounts of each lanthanide, which are also expected to provide different luminescence colors. [(EuyTb1−y)3(mCBL1)4(NO3)(DMF)x]n·solv (mCB- EuyTb1‑y) were obtained as needle-like crystals (Figure S1, Supporting Information) and in good yields (>64%) by following the solvothermal procedure employed for the single- Figure 3. Energy diagram of the singlet and triplet states calculated ion MOFs (see the Experimental Section for details). PXRD using TDDFT with the B3LYP functional. The orbitals involved in spectra for all mCB-EuyTb1−y compounds match very well with such processes of the mCBL1 ligand are shown. the individual mCB-Eu and mCB-Tb counterparts and 4798 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article Figure 4. (a) Photographs of the powders of the mixed mCB-EuyTb1−y (λex = 254 nm); (b) selection of steady-state emission spectra of the powders of mixed mCB-EuyTb1−y with various Eu/Tb molar ratios (λex = 280 nm) (see Figure S14 for the spectra of all mCB-EuyTb1−y series); (c) photograph of the hand-painted logo of the Institut de Ciència de Materials de Barcelona (ICMAB) with mCB-Tb (green), mCB-Eu0.1Tb0.9 (yellow), and mCB-Eu (red) crystals; and (d) color coordinates drawn onto the 1931 CIE chromaticity diagram for the mixed mCB-EuyTb1−y. Inset: luminescence microscopy images of the mCB-Tb (green), mCB-Eu0.1Tb0.9 (yellow), and mCB-Eu (red) crystals. Table 1. CIE Color Coordinates, Luminescence Lifetimes, Energy Transfer Efficiencies, Absolute Quantum Yield, and Emission Ratio for mCB-Eu, mCB-Tb, and mCB-EuyTb1−y (λex = 280 nm) τ (μs)a Ln CIE color coordinates 5 ( D4 of Tb ) 3+ (5D0 of Eu3+) ηTb→Eub (%) Φ (%) emission ratio of Eu/Tb Eu (0.62, 0.38) 739.0 20.5 ± 1.3 1.000/0.000 Eu0.6Tb0.4 (0.59, 0.33) 23.2 749.7 97.3 41.2 ± 2.1 0.997/0.003 Eu0.5Tb0.5 (0.58, 0.34) 60.2 859.6 92.9 42.5 ± 1.4 0.974/0.026 Eu0.25Tb0.75 (0.59, 0.34) 117.9 934.1 86.1 47.8 ± 2.0 0.971/0.029 Eu0.2Tb0.80 (0.57, 0.35) 219.3 1023.9 74.2 58.1 ± 2.8 0.949/0.051 Eu0.1Tb0.90 (0.58, 0.38) 331.6 1079.6 61.0 69.2 ± 2.6 0.849/0.151 Eu0.08Tb0.92 (0.55, 0.39) 465.1 1084.1 45.3 63.6 ± 2.3 0.825/0.175 Eu0.05Tb0.95 (0.44, 0.46) 575.0 1153.8 32.3 56.4 ± 2.7 0.516/0.484 Eu0.03Tb0.97 (0.39, 0.51) 676.4 1367.3 20.4 55.7 ± 1.7 0.248/0.752 Eu0.01Tb0.99 (0.36, 0.54) 818.3 1714.9 3.7 52.6 ± 2.5 0.230/0.770 Tb (0.32, 0.58) 849.7 49.8 ± 1.8 0.000/1.000 a Decay curves for mixed Ln-MOFs were fitted by a biexponential function (I = A1 exp(−t/τ1) + A2 exp(−t/τ2)), and the average lifetime was calculated from the equation of τ = (A1τ12 + A2τ22)/(A1τ1 + A2τ2).22,97 bEnergy transfer efficiency was determined by the function of ηTb→Eu = 1 − τ/τ0.96 therefore also proved to be also isostructural (Figure S3). The hand, the increase in the molar fraction of Eu from 0 to 0.08 in Eu/Tb molar ratios in the mixed MOFs were determined by the mixed Ln-MOF preparation caused a quite significant and inductively coupled plasma (ICP) measurements, revealing gradual shift of the emission color, from green (mCB-Tb) to that the ratios match reasonably well with the original molar orange (Figure 4b), as shown also by the corresponding CIE ratios of Eu3+/Tb3+ during the syntheses (Table S2). color coordinates and representative luminescence microscopy Steady-state irradiation (λex = 280 nm) of the obtained solid images (inset Figure 4d). However, a further increase of the Eu mCB-EuyTb1−y crystal powders yielded strong emission in the percentage (up to 100%) yielded less variation in the emission visible spectral region in all cases, with the emitted color finely ratios of the two elements in mCB-EuyTb1−y and thus a less and fully tunable between the two extreme colors (green and significant color change toward the red region of mCB-Eu. red) of the single-element Ln-MOFs (Figure 4a). This was ascribed to the negligible Tb emission contribution in A detailed analysis of the luminescence data for mCB- the mCB-EuyTb1−y crystals above a threshold Eu amount EuyTb1−y crystals (Table 1, Figures 4b and S14, Supporting (10%), as a consequence of an efficient Tb3+ energy transfer to Information) discloses some interesting results. On the one Eu3+ (Table 1). 4799 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article Figure 5. (a) Luminescence decays of Tb (λem = 541 nm) in the different MOFs (λexc = 280 nm); (b) luminescence decays of Eu (λem = 614 nm) in the different MOFs (λexc = 280 nm); (c) comparison of the luminescence decay of mCB-Eu0.6Tb0.4 with mCB-Eu; and (d) average lifetimes, ET quantum yield, and luminescence quantum yield trends against the Eu3+ fraction. These results indicate that the tunable emission in the mCB- changed to biexponential decay functions, with increasingly EuyTb1−y crystals is not only related to the additive relative shorter average decay times (Table 1 and Figures 5a and S16, luminescence of the Eu3+ and Tb3+ component elements but is Supporting Information). In contrast, in the emission curve of also the result of efficient energy transfer processes from Tb3+ Eu3+ of the mixed-metal MOFs, a signal increase at shorter to Eu3+,88,91−96,98 which results in an enhancement of the of times is followed by a luminescence decrease. The increasing Eu3+ luminescence instead of additive emissions from each ion. signal is slow for mCB-Eu0.01Tb0.99, but becomes shorter (i.e., These mixed-ion MOF crystals were successfully employed to faster) as the Eu3+ concentration increases, in good agreement prepare multicolored patterned luminescence drawings via with the lifetime decrease of the Tb3+ (Figures 5b and S17). hand-painting onto cellulose papers, which are colorless (i.e., The apparent increase of Eu3+ lifetimes at smaller concen- invisible crystals) under ambient light, while preserving the trations is the result of the convolution of the Eu3+ formation emission properties under UV radiation, making them highly and its luminescence decay. In mCB-Eu0.6Tb0.4, the signal rise suitable for anticounterfeiting technologies (Figure 4c). is so fast that the measured decay matches with the Further evidence of the Tb-Eu ET process is derived from monoexponential decay function and lifetime of the pure the study of the luminescence decays of Tb3+ and Eu3+ ions in Eu3+ MOF (Figure 5c). These results corroborate the ET all of the above compounds, registered at λem = 541 (5D4 → process between the Tb3+ and Eu3+, which becomes more 7 F5 of Tb3+) and 614 nm (5D0 → 7F2 of Eu3+), respectively, efficient as the concentration of Eu3+ increases, becoming upon pulsed light irradiation at λexc = 280 nm (Figures 5 and nearly quantitative (97.3%) in mCB-Eu0.6Tb0.4 (Figure 5c). S15−26, Supporting Information). Remarkably, the absolute quantum yields for mCB-EuyTb1−y The luminescence decay curves of mCB-Tb and mCB-Eu did not follow the same trend and varied greatly within these exhibited the typical monoexponential decay functions with mixed-metal MOFs: it increased passing from the values of the calculated lifetimes of 849.7 and 739.0 μs, respectively, which single-ion crystals mCB-Tb (49.8%) and mCB-Eu (20.5%) up are similar to those reported for other Eu- and Tb-based to a maximum of 69.2% in mCB-Eu0.1Tb0.90 (Table 1 and compounds (Table 1 and Figure S15, Supporting Informa- Figure 5d), which represents an outstanding increase of 237% tion).90 The emission decay curves of Tb3+ in mCB-EuyTb1−y, of the quantum yield of that for mCB-Eu (20.5%) or an 4800 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article increase of 39% with respect to that for mCB-Tb (49.8%). though they yielded greener coordinates at shorter delay times Such a huge enhancement of the overall quantum yield reveals (0.33, 0.60) and a yellow color at longer delays (0.42, 0.52). that the ligand-to-Tb3+ and Tb3+-to-Eu3+ consecutive energy The different range of color variation for this compound was transfers are much more efficient than the direct ligand-to-Eu3+ ascribed to the slower Tb3+−Eu3+ energy transfer process that energy transfer. However, when the Eu3+ amount increases delays the loss of the green emission of Tb3+, which thus significantly (20%), it starts competing with Tb3+ in the ET contributes significantly to the overall spectra until the end of transfer from the ligand, lowering the overall quantum yield the luminescence (Figure 7a). The opposite effect was (Figure 6). The observed energy transfer process is well known observed for the mCB-Eu0.60Tb0.40 crystals, which showed to happen within these two metals, although such an increase time-dependent emission spectra changing from yellow (0.49, in the quantum yield has not been reported.88,91−96 0.49) to red (0.59, 0.36), as shown in Figure 7c. In this case, by the time the first spectrum is recorded, the emission contribution of Tb3+ is already partially merged with the sensitized Eu3+ emission, providing the yellow coloring. Moreover, Tb3+ emission is, in this case, quickly quenched, yielding delayed emission spectra with only the red contribution of Eu3+. Therefore, these materials not only show time-dependent emission spectra and color coordinates but also enable the emission color range to be changed (and the starting and ending point) by simply modifying the stoichiometry of the ions. This time-dependent color change, observed in all mixed mCB-EuyTb1−y, introduces more complexity to the luminescence color tunability through the relative proportion of Eu3+/Tb3+. Time-Dependent Bar-Coding. For the second feature, we explored the possibility of using the discrete and narrow Figure 6. Schematic diagram of the energy absorption to the singlet emission bands of lanthanide ions to obtain time-dependent state (S0) of the mCBL1 ligand, transfer to the triplet state (T1), bar-coding. For this, we performed pulsed measurements of energy transfer, and emission processes of mCB-EuyTb1−y. the three compounds above, recording the projection of the emitted photons over time onto the detecting matrix of a Time-Dependent Optical Properties of mCB-EuyTb1−y charge-coupled device (CCD) camera. Taking advantage of Crystals for Anticounterfeiting. A precise tailoring of a the different decay profiles and rates of Tb3+ (emission lifetime at an emission band can entail a virtually unlimited decrease after the pulse) and Eu3+ (increase and then number of unique temporal codes.99 However, to date, a few decrease), luminescent bar-coding changing the number and reports have considered Ln-MOFs for lifetime-based encoding relative intensities of the lines (associated with the emitted in the visible range for optical multiplexing,27,98,100 but tunable bands of the two ions) was obtained (Figures 7g−i and S27− fluorescent lifetime has not been proposed for anticounterfeit- S29, Supporting Information). It is easy to understand the ing. The energy transfer process between Eu3+ and Tb3+ ions relevance of this time-dependent bar-coding to create dynamic and the control of their decay rates in different mCB-EuyTb1−y security messages and labels changing the provided informa- crystals allowed us to explore two optical features of interest tion in a microsecond−millisecond time scale. For mCB- for anticounterfeiting technologies for the first time: time- Eu0.1Tb0.90, the initial and final bar-code lines are related to the dependent emission color change and time-dependent bar- emission bands of nearly pure Tb3+ or Eu3+, respectively coding. These were demonstrated for mCB-Eu0.01Tb0.99, mCB- (Figures 7h and S28, Supporting Information). This means Eu0.1Tb0.90, and mCB-Eu0.60Tb0.40 crystals where the lumines- that the coded information changes all of the time along the cence lifetime variation of Eu3+ and Tb3+ is achieved by recorded time frame. In the case of mCB-Eu0.01Tb0.99 (slower changing the metal stoichiometry in mCB-EuyTb1−y. ET), the emission of Eu3+ only starts appearing after 500 μs, Time-Dependent Emission Spectra (and Color). These which means the coded information only starts changing at were recorded at various delay times (0.5−10 000 μs) upon later delays (Figures 7g and S27, Supporting Information). irradiation with a 266 nm pulsed neodymium-doped yttrium Finally, for the mCB-Eu0.60Tb0.40 powder (fast ET), the Tb3+ aluminum garnet (Nd-YAG) laser (Figure 7a−f). The spectra lines only slightly appear for the first few microseconds, which measured for the mCB-Eu0.1Tb0.90 crystals gradually changed means the coding information will not change further after a from green (0.40, 0.56) to red (0.61, 0.37) (Figure 7b), short delay time (Figures 7i and S29, Supporting Information). following a similar color variation trend registered under Similar results were obtained on irradiating with lower-energy continuous-wave irradiation for MOFs made of different ion excitation wavelengths (355 nm, Figures S30 and S32, compositions. In this case, different colors were obtained from Supporting Information). a single MOF at different delay times. The green color These very promising results pushed us to use these observed at shorter delays was due to the Tb3+ emission, which encoding materials for printing onto cellulose papers to was still not quenched efficiently by Eu3+. The red color simultaneously obtain time-dependent luminescent colors recorded at longer delays was ascribed to the Eu3+ emission and codes onto patterned spatial domains, which will bring after Tb 3+ was fully quenched (complete ET). The new schemes for advanced anticounterfeiting technologies and intermediate colors were the result of the contribution of security data storage. Printing was carried out through a both the sensitized Eu3+ and the still not quenched Tb3+. When custom-made spray-coating technique in which a prefabricated the same study was carried out for the mCB-Eu0.01Tb0.99 mask with a logo was layered onto the substrate under the powder, time-dependent emission spectra were still recorded, nozzle (Figure S33, Supporting Information). The printed 4801 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article Figure 7. Time-dependent emission spectra of (a) mCB-Eu0.01Tb0.99, (b) mCB-Eu0.1Tb0.9, and (c) mCB-Eu0.6Tb0.4 powders at various time delays and (d−f) corresponding CIE coordinates (λex = 266 nm). Time-dependent bar codes of (g) mCB-Eu0.01Tb0.99, (h) mCB-Eu0.1Tb0.9, and (i) mCB-Eu0.6Tb0.4 (λex = 355 nm). colorless cellulose paper showed no patterns under daylight spectra (Figure S34) yielded an orange color with coordinates while preserving the emission properties under UV radiation. at (0.57, 0.38) in the CIE 1931 color space diagram as the Under continuous-wave UV irradiation, the printed pattern can crystal powder (Figure 4b). However, measurements under be recognized (Figure 8a). The recorded steady-state emission pulsed irradiation (266 nm) revealed time-dependent 4802 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article Figure 8. (a) Spray-coated mCB-Eu0.01Tb0.99 using a prepatterned mask to illustrate the logo on Institut de Nanociencia i Nanotecnologia, (b) time-dependent emission spectra of the printed mCB-Eu0.01Tb0.99, (c) corresponding color coordinates in the 1931 CIE diagram, and (d) time- dependent bar codes of the printed mCB-Eu0.01Tb0.99 (λex = 355 nm). luminescent spectra (Figure 8b), color (Figure 8c), and bar highly attractive for dynamic color-changing security inks in codes (Figures 8d and S31), confirming that the optical anticounterfeiting technologies. ■ properties of the powder are preserved after printing in cellulose papers, the substrate most used for sensitive EXPERIMENTAL SECTION documents. ■ All chemicals were of reagent-grade quality. They were purchased from commercial sources and used as received. A 1,7-di(4- CONCLUSIONS carboxyphenyl)-1,7-dicarba-closo-dodecaborane ligand (mCBH2L1) was synthesized according to the literature procedure.101 Herein, we report carborane ligand-based Ln-MOFs (also Synthesis of {[(Ln)3(mCBL1)4(NO3)(DMF)n]·Solv} (mCB-Ln, known as lanthanide coordination polymers [Ln-CPs]) as a Where Ln = Eu, Tb, and EuxTb1−x). The mCB-Ln materials were novel class of water- and temperature-stable materials that prepared by solvothermal synthesis. In a typical preparation, exhibit multimodal luminescence tunability. We have synthe- mCBH2L1 (0.03 mmol) and Ln(NO3)3 (0.02 mmol; Ln = Eu, Ln) sized and fully characterized a new family of isostructural were added to a mixture of DMF (0.5 mL)/methanol (1.5 mL)/H2O mCB-EuyTb1−y (y = 0−1) luminescence MOFs built on a (0.3 mL) and sonicated until complete dissolution of all reagents. The above mixture was transferred to an 8 dram vial and heated at 95 °C highly hydrophobic carborane linker (mCBL1). Ln-MOFs in an oven for 48 h. Needle-like white crystals were collected and prepared from Eu3+ and Tb3+ at different ratios permitted easy washed with DMF (yield based on the lanthanides: 71% for mCB-Tb modulation of the luminescence from the green to the red and 64% for mCB-Eu). IR (ATR; selected bands; cm−1): 2601 (BH); region of the 1931 CIE lab space diagram. This color tunability 1658 (CO from DMF); and 1590 (CO from carboxylate). was ascribed to the controlled energy transfer (ET) efficiency Elemental analysis (%) calculated for [Eu3(mCB-L)4(NO3)(DMF)2]· between Tb3+ and Eu3+. The ET process was corroborated by 6H2O: C 36.23, H 4.14, N 2.07; found: C 36.36, H, 4.24, N 1.82. both spectral measurements and lifetime decays, which showed Elemental analysis (%) calculated for [Tb3(mCB-L)4(NO3)(DMF)2]· nearly quantitative ET efficiency when the Eu3+ was increased 6H2O: C 36.23, H 4.14, N 2.07; found: C 36.16, H, 4.31, N 1.66. The mixed mCB-EuxTb1−x materials were prepared using the same to 60%. The different lifetimes of Tb+ and Eu3+ in each MOF method by adjusting the ratios of Eu(NO3)3/Tb(NO3)3 salts. also allowed time-dependent spectral changes in the ms time Preparation of the Multimodal Anticounterfeiting Model. scale to be obtained. An outstanding increase of 237% of the Anticounterfeiting tags were painted using fluorescent inks with an quantum yield of mCB-Eu (20.5%) in the mixed mCB- optimized concentration of Ln-MOFs (0.2 mg/mL). To prepare the Eu0.1Tb0.9 (69.2%) is achieved, along with an increased and aqueous security inks, crystals of Ln-MOFs were manually ground and tunable lifetime luminescence (from about 10 to 10000 μs), all then dispersed in water with the help of ultrasonication. A of these promoted by a highly effective ET process. Moreover, commercially available filter paper was used as a substrate in this study. A handwritten image was obtained using a stick contaminated taking advantage of the narrow bands of Ln, we were able to with the security inks. To get a more regular printing pattern, a obtain time-dependent bar codings, whose bars and the rate of custom-made spray-coating technique was employed, in which a change could be modulated by the MOF composition. prefabricated mask with a logo was layered onto the substrate under These results, together with the fact that these particles the nozzle (Figure S31). It should be mentioned that the could be printed through spray-coating, make these materials luminescence intensity of the inks and the subsequently printed 4803 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article patterns could be easily adjusted by varying the concentration of Ln- hydrogen atoms were included because they provide a better MOFs. description of the metal-coordinated ligands than the anionic ligands. Instruments and Characterization. A crystal suitable for single- crystal X-ray diffraction (SCXRD) with dimensions 0.18 × 0.07 × 0.04 mm3 was selected and mounted on a MITIGEN holder with silicon oil on a ROD, Synergy Custom system, HyPix diffractometer. ■ * ASSOCIATED CONTENT sı Supporting Information The crystal was kept at a steady T = 100(2) K during data collection. The Supporting Information is available free of charge at The structure was solved with the ShelXT 2014/5102 solution https://pubs.acs.org/doi/10.1021/acs.chemmater.2c00323. program using dual methods and using Olex2 1.5-α103 as the graphical Optical and SEM images, IR, TGA, crystallographic interface. The model was refined with ShelXL 2016/6104 using full- data, powder X-ray diffraction, UV−vis spectra, matrix least-squares minimization on F2. The structure is refined in luminescence spectra and decay curves, TTDFT results, the monoclinic space-group Pn with a β angle of 90.094(1)° and a and time-dependent emission spectra (PDF) ■ twin law replicating orthorhombic symmetry (100, 01̅0, 001̅), BASF = 0.43. The DMF molecules were refined as rigid groups with various thermal parameter restraints. Attenuated total reflection Fourier AUTHOR INFORMATION transform infrared (ATR-FTIR) spectra were recorded using a Corresponding Authors PerkinElmer Spectrum One spectrometer equipped with a Universal Claudio Roscini − Catalan Institute of Nanoscience and ATR sampling accessory. Spectra were collected with a 2 cm−1 Nanotechnology (ICN2), CSIC, and The Barcelona Institute spectral resolution in the 4000−650 cm−1 range. Elemental analyses of Science and Technology (BIST), Bellaterra, Barcelona were obtained using a Thermo (Carlo Erba) Flash 2000 Elemental Analyzer, configured for wt % CHN. Thermogravimetric analysis 08193, Spain; orcid.org/0000-0002-0157-8934; (TGA) was performed in N2, on an nSTA 449 F1 Jupiter instrument Email: claudio.roscini@icn2.cat (heating rate: 10 °C/min; temperature range: 25−800 °C). Powder José Giner Planas − Institut de Ciència de Materials de X-ray diffraction (PXRD) was recorded at room temperature on a Barcelona (ICMAB-CSIC), 08193 Bellaterra, Spain; Siemens D-5000 diffractometer with Cu Kα radiation (λ = 1.5418 Å, orcid.org/0000-0002-1648-2169; Email: jginerplanas@ 35 kV, 35 mA, increment = 0.02°). Inductively coupled plasma-mass icmab.es spectrometry (ICP-MS) measurements were carried out on an Agilent ICP-MS 7700x apparatus. Scanning electron microscopy (SEM) Authors (QUANTA FEI 200 FEGESEM) and optical microscopy (Olympus Zhen Li − Institut de Ciència de Materials de Barcelona BX52) were used to monitor the morphology and color changes at (ICMAB-CSIC), 08193 Bellaterra, Spain various conditions. Solid-state UV−visible spectra were obtained on a Rosario Núñez − Institut de Ciència de Materials de UV−Vis−NIR V-780 spectrophotometer equipped with an opera- Barcelona (ICMAB-CSIC), 08193 Bellaterra, Spain; tional range of 200−1600 nm. orcid.org/0000-0003-4582-5148 Emission spectra were obtained with a PTI Quantamaster 300 Mark E. Light − Department of Chemistry, University of fluorimeter, putting the solid powder in a custom-made holder and Southampton, Highfield, Southampton SO17 1BJ, U.K. setting the holder plane at 45° with the direction of the incident light and the optical path toward the detector. All spectra were obtained on Eliseo Ruiz − Departament de Química Inorgànica i Orgànica irradiating with a continuous-wave Xe lamp at λexc = 280 nm. Lifetime and Institut de Recerca de Química Teòrica i Computacional, measurements were obtained with the same fluorimeter, but at an Universitat de Barcelona, 08028 Barcelona, Spain; excitation of 280 nm with a pulsed Xe lamp (100 Hz, 2 μs integration orcid.org/0000-0001-9097-8499 time). Absolute luminescence quantum yields (Φ) of solid-state Francesc Teixidor − Institut de Ciència de Materials de samples under continuous-wave excitation (λex = 280 nm) were Barcelona (ICMAB-CSIC), 08193 Bellaterra, Spain; determined using the quantum yield fluorimeter Hamamatsu C9920- orcid.org/0000-0002-3010-2417 02G, equipped with an integrating sphere, connected to the lamp with Clara Viñas − Institut de Ciència de Materials de Barcelona an optical fiber, at room temperature in the air. Φ values were (ICMAB-CSIC), 08193 Bellaterra, Spain; orcid.org/ calculated based on the number of photons absorbed and emitted by 0000-0001-5000-0277 the sample. A detailed measurement procedure can be found in a Daniel Ruiz-Molina − Catalan Institute of Nanoscience and previous report.97 Reported overall Φ values are averages of at least three independent determinations. Nanotechnology (ICN2), CSIC, and The Barcelona Institute Delay time-dependent emission spectra and bar codes under a of Science and Technology (BIST), Bellaterra, Barcelona pulsed excitation (λex = 355 and 266 nm) were recorded irradiating 08193, Spain; orcid.org/0000-0002-6844-8421 with the fourth and third harmonic of a Nd:YAG (Brilliant B, Spectra Complete contact information is available at: Physics) ns pulsed laser. The emission was recorded using an Andor https://pubs.acs.org/10.1021/acs.chemmater.2c00323 ICCD camera coupled to a spectrograph, setting the sample powder or loaded cellulose papers at 45° with the incident beam and the Author Contributions optical path toward the detector. Measurements were recorded at a 1 Hz frequency, 100 ns (266 nm) or 5000 ns (355 nm) integration This manuscript was written through contributions of all time, and applying different delays with respect to the excitation pulse. authors. All authors have given approval to the final version of Computational Details. To analyze the photochemical properties the manuscript. of the mCB ligand, computational methods have been employed. The Notes calculations were performed using the Gaussian 16 program105 with The authors declare no competing financial interest. ■ the TDDFT method and the exchange−correlation functional B3LYP.106 Other functionals commonly employed in the TDDFT ACKNOWLEDGMENTS calculation of organic systems were tested (PBE0,107 LC-wPBE108). However, due to the larger exact exchange contributions, they provide This work was financially supported by the MINECO a more energetic transition than B3LYP and consequently, poorer (PID2019-106832RB-I00), MICINN through the Severo agreement with the experimental data. The 6-311G* basis set was Ochoa Program for Centers of Excellence for the FUNFU- employed for the geometry optimization and the 6-311+G** basis set TURE (CEX2019-000917-S, MDM-2017-0767, and SEV- for the TDDFT calculations. Neutral molecules including the acidic 2017-0706 projects), grant RTI2018-098027-B-C21 funded 4804 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article by MCIN/AEI/10.13039/501100011033 and by ERDF A way Coordination Polymers, MOFs and Functional Nanomaterials. Dalton of making Europe and the Generalitat de Catalunya (2017/ Trans. 2021, 50, 770−784. SGR/1720 and SGR2017-1289). Z.L. is enrolled in the UAB (22) Nguyen, T. N.; Eliseeva, S. V.; Gładysiak, A.; Petoud, S.; Ph.D. program and acknowledges the China Scholarship Stylianou, K. C. Design of Lanthanide-Based Metal−Organic Frameworks with Enhanced near-Infrared Emission. J. Mater. Chem. Council (CSC) for his Ph.D. grant (201808310071). ■ A 2020, 8, 10188−10192. (23) Li, Z.; Liu, X.; Wang, G.; Li, B.; Chen, H.; Li, H.; Zhao, Y. REFERENCES Photoresponsive Supramolecular Coordination Polyelectrolyte as (1) Long, J. R.; Yaghi, O. M. The Pervasive Chemistry of Metal- Smart Anticounterfeiting Inks. Nat. Commun. 2021, 12, No. 1363. Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1213−1214. (24) Abdollahi, A.; Roghani-Mamaqani, H.; Razavi, B.; Salami- (2) Kitagawa, S.; Kitaura, R.; Noro, S. Functional Porous Kalajahi, M. Photoluminescent and Chromic Nanomaterials for Coordination Polymers. Angew. Chem., Int. Ed. 2004, 43, 2334−2375. Anticounterfeiting Technologies: Recent Advances and Future (3) James, S. L. Metal-Organic Frameworks. Chem. Soc. Rev. 2003, Challenges. ACS Nano 2020, 14, 14417−14492. 32, 276−288. (25) Gao, Z.; Yang, S.; Xu, B.; Zhang, T.; Chen, S.; Zhang, W.; Sun, (4) Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Design and X.; Wang, Z.; Wang, X.; Meng, X.; Zhao, Y. S. Laterally Engineering Synthesis of an Exceptionally Stable and Highly Porous Metal- Lanthanide-MOFs Epitaxial Heterostructures for Spatially Resolved Organic Framework. Nature 1999, 402, 276−279. Planar 2D Photonic Barcoding. Angew. Chem. 2021, 133, 24724− (5) Dhaka, S.; Kumar, R.; Deep, A.; Kurade, M. B.; Ji, S.-W.; Jeon, 24730. B.-H. Metal−Organic Frameworks (MOFs) for the Removal of (26) Pei, K.; Wu, J.; Zhao, M.; Feng, X.; Li, Y.; Ma, Y.; Li, H.; Zhai, Emerging Contaminants from Aquatic Environments. Coord. Chem. T. Polarized Emission of Lanthanide Metal−Organic Framework (Ln- Rev. 2019, 380, 330−352. MOF) Crystals for High-Capacity Photonic Barcodes. Adv. Opt. (6) Du, M.; Li, Q.; Zhao, Y.; Liu, C.-S.; Pang, H. A Review of Mater. 2022, 10, No. 2102143. Electrochemical Energy Storage Behaviors Based on Pristine Metal− (27) Zhou, H.; Han, J.; Cuan, J.; Zhou, Y. Responsive Luminescent Organic Frameworks and Their Composites. Coord. Chem. Rev. 2020, MOF Materials for Advanced Anticounterfeiting. Chem. Eng. J. 2022, 416, No. 213341. 431, No. 134170. (7) Rojas, S.; Horcajada, P. Metal−Organic Frameworks for the (28) Burtch, N. C.; Jasuja, H.; Walton, K. S. Water Stability and Removal of Emerging Organic Contaminants in Water. Chem. Rev. Adsorption in Metal−Organic Frameworks. Chem. Rev. 2014, 114, 2020, 120, 8378−8415. 10575−10612. (8) Czaja, A. U.; Trukhan, N.; Müller, U. Industrial Applications of (29) Rieth, A. J.; Hunter, K. M.; Dincă, M.; Paesani, F. Hydrogen Metal−Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1284−1293. Bonding Structure of Confined Water Templated by a Metal-Organic (9) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Luminescent Functional Framework with Open Metal Sites. Nat. Commun. 2019, 10, Metal-Organic Frameworks. Chem. Rev. 2012, 112, 1126−1162. No. 4771. (10) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The (30) Ding, M.; Cai, X.; Jiang, H.-L. Improving MOF Stability: Chemistry and Applications of Metal-Organic Frameworks. Science Approaches and Applications. Chem. Sci. 2019, 10, 10209−10230. 2013, 341, No. 1230444. (31) Yuan, S.; Feng, L.; Wang, K.; Pang, J.; Bosch, M.; Lollar, C.; (11) Wang, H.; Zhu, Q.-L.; Zou, R.; Xu, Q. Metal-Organic Sun, Y.; Qin, J.; Yang, X.; Zhang, P.; Wang, Q. Stable Metal−Organic Frameworks for Energy Applications. Chem 2017, 2, 52−80. Frameworks: Design, Synthesis, and Applications. Adv. Mater. 2018, (12) Lustig, W. P.; Mukherjee, S.; Rudd, N. D.; Desai, A. V.; Li, J.; 30, No. 1704303. Ghosh, S. K. Metal−Organic Frameworks: Functional Luminescent (32) Zhang, X.; Wang, B.; Alsalme, A.; Xiang, S.; Zhang, Z.; Chen, B. and Photonic Materials for Sensing Applications. Chem. Soc. Rev. Design and Applications of Water-Stable Metal-Organic Frameworks: 2017, 46, 3242−3285. Status and Challenges. Coord. Chem. Rev. 2020, 423, No. 213507. (13) Espallargas, G. M.; Coronado, E. Magnetic Functionalities in (33) Liu, X.; Wang, X.; Kapteijn, F. Water and Metal−Organic MOFs: From the Framework to the Pore. Chem. Soc. Rev. 2018, 47, Frameworks: From Interaction toward Utilization. Chem. Rev. 2020, 533−557. 120, 8303−8377. (14) Armelao, L.; Quici, S.; Barigelletti, F.; Accorsi, G.; Bottaro, G.; (34) Duan, J.; Jin, W.; Kitagawa, S. Water-Resistant Porous Cavazzini, M.; Tondello, E. Design of Luminescent Lanthanide Coordination Polymers for Gas Separation. Coord. Chem. Rev. 2017, Complexes: From Molecules to Highly Efficient Photo-Emitting 332, 48−74. Materials. Coord. Chem. Rev. 2010, 254, 487−505. (35) Gelfand, B. S.; Shimizu, G. K. H. Parameterizing and Grading (15) Xing, S.; Janiak, C. Design and Properties of Multiple-Emitter Hydrolytic Stability in Metal−Organic Frameworks. Dalton Trans. Luminescent Metal−Organic Frameworks. Chem. Commun. 2020, 56, 2016, 45, 3668−3678. 12290−12306. (36) Yu, H.; Liu, Q.; Li, J.; Su, Z.-M.; Li, X.; Wang, X.; Sun, J.; Zhou, (16) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Luminescent Functional C.; Hu, X. A Dual-Emitting Mixed-Lanthanide MOF with High Metal−Organic Frameworks. Chem. Rev. 2012, 112, 1126−1162. Water-Stability for Ratiometric Fluorescence Sensing of Fe3+ and (17) Eliseeva, S. V.; Bünzli, J.-C. G. Lanthanide Luminescence for Ascorbic Acid. J. Mater. Chem. C 2021, 9, 562−568. Functional Materials and Bio-Sciences. Chem. Soc. Rev. 2010, 39, (37) Plesek, J. Potential Applications of the Boron Cluster 189−227. Compounds. Chem. Rev. 1992, 92, 269−278. (18) Rocha, J.; Carlos, L. D.; Paz, F. A. A.; Ananias, D. Luminescent (38) Scholz, M.; Hey-Hawkins, E. Carbaboranes as Pharmaco- Multifunctional Lanthanides-Based Metal−Organic Frameworks. phores: Properties, Synthesis, and Application Strategies. Chem. Rev. Chem. Soc. Rev. 2011, 40, 926−940. 2011, 111, 7035−7062. (19) Younis, S. A.; Bhardwaj, N.; Bhardwaj, S. K.; Kim, K.-H.; Deep, (39) Grimes, R. N. Carboranes; Grimes, R. N., Ed.; Academic Press, A. Rare Earth Metal−Organic Frameworks (RE-MOFs): Synthesis, 2016. Properties, and Biomedical Applications. Coord. Chem. Rev. 2021, (40) Teixidor, F.; Kaufmann, D. E. Science of Synthesis: Houben-Weyl 429, No. 213620. Methods of Molecular Transformations, 5th ed.; Mulzer, Ed.; Georg (20) Saraci, F.; Quezada-Novoa, V.; Donnarumma, P. R.; Howarth, Thieme Verlag: Stuttgart, 2015; Vol. 6. A. J. Rare-Earth Metal−Organic Frameworks: From Structure to (41) Fujii, S. Expanding the Chemical Space of Hydrophobic Applications. Chem. Soc. Rev. 2020, 49, 7949−7977. Pharmacophores: The Role of Hydrophobic Substructures in the (21) Gorai, T.; Schmitt, W.; Gunnlaugsson, T. Highlights of the Development of Novel Transcription Modulators. MedChemComm Development and Application of Luminescent Lanthanide Based 2016, 7, 1082−1092. 4805 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article (42) Issa, F.; Kassiou, M.; Rendina, L. M. Boron in Drug Discovery: (58) Rodríguez-Hermida, S.; Tsang, M. Y.; Vignatti, C.; Stylianou, K. Carboranes as Unique Pharmacophores in Biologically Active C.; Guillerm, V.; Pérez-Carvajal, J.; Teixidor, F.; Viñ as, C.; Compounds. Chem. Rev. 2011, 111, 5701−5722. Choquesillo-Lazarte, D.; Verdugo-Escamilla, C.; Peral, I.; Juanhuix, (43) Valliant, J. F.; Guenther, K. J.; King, A. S.; Morel, P.; Schaffer, J.; Verdaguer, A.; Imaz, I.; Maspoch, D.; Giner Planas, J. Switchable P.; Sogbein, O. O.; Stephenson, K. A. The Medicinal Chemistry of Surface Hydrophobicity-Hydrophilicity of a Metal-Organic Frame- Carboranes. Coord. Chem. Rev. 2002, 232, 173−230. work. Angew. Chem., Int. Ed. 2016, 55, 16049−16053. (44) Farha, O. K.; Spokoyny, A. M.; Mulfort, K. L.; Hawthorne, M. (59) Tsang, M. Y.; Rodríguez-Hermida, S.; Stylianou, K. C.; Tan, F.; F.; Mirkin, C. A.; Hupp, J. T. Synthesis and Hydrogen Sorption Negi, D.; Teixidor, F.; Viñas, C.; Choquesillo-Lazarte, D.; Verdugo- Properties of Carborane Based Metal−Organic Framework Materials. Escamilla, C.; Guerrero, M.; Sort, J.; Juanhuix, J.; Maspoch, D.; Giner J. Am. Chem. Soc. 2007, 129, 12680−12681. Planas, J. Carborane Bis-Pyridylalcohols as Linkers for Coordination (45) Bae, Y.-S.; Farha, O. K.; Spokoyny, A. M.; Mirkin, C. A.; Hupp, Polymers: Synthesis, Crystal Structures, and Guest-Framework J. T.; Snurr, R. Q. Carborane-Based Metal−Organic Frameworks as Dependent Mechanical Properties. Cryst. Growth Des. 2017, 17, Highly Selective Sorbents for CO2 over Methane. Chem. Commun. 846−857. 2008, No 35, 4135. (60) Tan, F.; López-Periago, A.; Light, M. E.; Cirera, J.; Ruiz, E.; (46) Farha, O. K.; Spokoyny, A. M.; Mulfort, K. L.; Galli, S.; Hupp, Borrás, A.; Teixidor, F.; Viñas, C.; Domingo, C.; Planas, J. G. An J. T.; Mirkin, C. A. Gas-Sorption Properties of Cobalt(II)− Unprecedented Stimuli-Controlled Single-Crystal Reversible Phase Carborane-Based Coordination Polymers as a Function of Morphol- Transition of a Metal−Organic Framework and Its Application to a ogy. Small 2009, 5, 1727−1731. Novel Method of Guest Encapsulation. Adv. Mater. 2018, 30, (47) Bae, Y.-S.; Spokoyny, A. M.; Farha, O. K.; Snurr, R. Q.; Hupp, No. 1800726. J. T.; Mirkin, C. A. Separation of Gas Mixtures Using Co(Ii) (61) Gan, L.; Chidambaram, A.; Fonquernie, P. G.; Light, M. E.; Carborane-Based Porous Coordination Polymers. Chem. Commun. Choquesillo-Lazarte, D.; Huang, H.; Solano, E.; Fraile, J.; Viñas, C.; 2010, 46, 3478−3480. Teixidor, F.; Navarro, J. A. R.; Stylianou, K. C.; Planas, J. G. A Highly (48) Spokoyny, A. M.; Farha, O. K.; Mulfort, K. L.; Hupp, J. T.; Water-Stable Meta -Carborane-Based Copper Metal−Organic Frame- Mirkin, C. A. Porosity Tuning of Carborane-Based Metal−Organic work for Efficient High-Temperature Butanol Separation. J. Am. Frameworks (MOFs) via Coordination Chemistry and Ligand Chem. Soc. 2020, 142, 8299−8311. Design. Inorg. Chim. Acta 2010, 364, 266−271. (62) Li, Z.; Fraile, J.; Viñas, C.; Teixidor, F.; Planas, J. G. Post- (49) Huang, S.-L.; Lin, Y.-J.; Yu, W.-B.; Jin, G.-X. Porous Synthetic Modification of a Highly Flexible 3D Soft Porous Metal− Frameworks Based on Carborane-Ln2(CO2)6: Architecture Influ- Organic Framework by Incorporating Conducting Polypyrrole: enced by Lanthanide Contraction and Selective CO2 Capture. Enhanced MOF Stability and Capacitance as an Electrode Material. ChemPlusChem 2012, 77, 141−147. Chem. Commun. 2021, 57, 2523−2526. (50) Kennedy, R. D.; Krungleviciute, V.; Clingerman, D. J.; (63) Li, Z.; Choquesillo-Lazarte, D.; Fraile, J.; Viñas, C.; Teixidor, Mondloch, J. E.; Peng, Y.; Wilmer, C. E.; Sarjeant, A. A.; Snurr, R. F.; Planas, J. G. Rational Design of Carborane-Based Cu 2 -Paddle Q.; Hupp, J. T.; Yildirim, T.; Farha, O. K.; Mirkin, C. A. Carborane- Wheel Coordination Polymers for Increased Hydrolytic Stability. Dalton Trans. 2022, 51, 1137−1143. Based Metal−Organic Framework with High Methane and Hydrogen (64) Teixidor, F.; Barberà, G.; Vaca, A.; Kivekäs, R.; Sillanpää, R.; Storage Capacities. Chem. Mater. 2013, 25, 3539−3543. Oliva, J.; Viñas, C. Are Methyl Groups Electron-Donating or (51) Clingerman, D. J.; Morris, W.; Mondloch, J. E.; Kennedy, R. D.; Electron-Withdrawing in Boron Clusters? Permethylation of o- Sarjeant, A. A.; Stern, C.; Hupp, J. T.; Farha, O. K.; Mirkin, C. A. Carborane. J. Am. Chem. Soc. 2005, 127, 10158−10159. Stabilization of a Highly Porous Metal−Organic Framework Utilizing (65) Poater, J.; Viñas, C.; Bennour, I.; Escayola, S.; Solà, M.; a Carborane-Based Linker. Chem. Commun. 2015, 51, 6521−6523. Teixidor, F. Too Persistent to Give Up: Aromaticity in Boron Clusters (52) Planas, J.; Teixidor, F.; Viñas, C. N,O-Type Carborane-Based Survives Radical Structural Changes. J. Am. Chem. Soc. 2020, 142, Materials. Crystals 2016, 6, 50. 9396−9407. (53) Di Salvo, F.; Paterakis, C.; Tsang, M. Y.; Garcia, Y.; Viñas, C.; (66) Bellomo, C.; Zanetti, D.; Cardano, F.; Sinha, S.; Chaari, M.; Teixidor, F.; Giner Planas, J.; Light, M. E.; Hursthouse, M. B.; Fin, A.; Maranzana, A.; Núñez, R.; Blangetti, M.; Prandi, C. Red Choquesillo-Lazarte, D. Synthesis and Crystallographic Studies of Light-Emitting Carborane-BODIPY Dyes: Synthesis and Properties of Disubstituted Carboranyl Alcohol Derivatives: Prevailing Chiral Visible-Light Tuned Fluorophores with Enhanced Boron Content. Recognition? Cryst. Growth Des. 2013, 13, 1473−1484. Dyes Pigm. 2021, 194, No. 109644. (54) Di Salvo, F.; Tsang, M. Y.; Teixidor, F.; Viñas, C.; Planas, J. G.; (67) Ferrer-Ugalde, A.; González-Campo, A.; Planas, J. G.; Viñas, C.; Crassous, J.; Vanthuyne, N.; Aliaga-Alcalde, N.; Ruiz, E.; Coquerel, Teixidor, F.; Sáez, I. M.; Núñez, R. Tuning the Liquid Crystallinity of G.; Clevers, S.; Dupray, V.; Choquesillo-Lazarte, D.; Light, M. E.; Cholesteryl-o-Carborane Dyads: Synthesis, Structure, Photolumines- Hursthouse, M. B. A Racemic and Enantiopure Unsymmetric cence, and Mesomorphic Properties. Crystals 2021, 11, 133. Diiron(III) Complex with a Chiral o-Carborane-Based Pyridylalcohol (68) Chaari, M.; Kelemen, Z.; Choquesillo-Lazarte, D.; Ligand: Combined Chiroptical, Magnetic, and Nonlinear Optical Gaztelumendi, N.; Teixidor, F.; Viñas, C.; Nogués, C.; Núñez, R. Properties. Chem. - Eur. J. 2014, 20, 1081−1090. Efficient Blue Light Emitting Materials Based on M-Carborane− (55) Tsang, M. Y.; Viñas, C.; Teixidor, F.; Planas, J. G.; Conde, N.; Anthracene Dyads. Structure, Photophysics and Bioimaging Studies. SanMartin, R.; Herrero, M. T.; Dominguez, E.; Lledos, A.; Vidossich, Biomater. Sci. 2019, 7, 5324−5337. P.; Choquesillo-Lazarte, D. Synthesis, Structure, and Catalytic (69) Bellomo, C.; Chaari, M.; Cabrera-González, J.; Blangetti, M.; Applications for Ortho- and Meta-Carboranyl Based NBN Pincer- Lombardi, C.; Deagostino, A.; Viñas, C.; Gaztelumendi, N.; Nogués, Pd Complexes. Inorg. Chem. 2014, 53, 9284−9295. C.; Nuñ ez, R.; Prandi, C. Carborane-BODIPY Dyads: New (56) Tsang, M. Y.; Teixidor, F.; Viñas, C.; Choquesillo-Lazarte, D.; Photoluminescent Materials through an Efficient Heck Coupling. Aliaga-Alcalde, N.; Planas, J. G. Synthesis, Structures and Properties Chem. - Eur. J. 2018, 24, 15622−15630. of IronIII Complexes with (o-Carboranyl)Bis-(2-Hydroxymethyl)- (70) Chaari, M.; Kelemen, Z.; Planas, J. G.; Teixidor, F.; Pyridine: Racemic versus Meso. Inorg. Chim. Acta 2016, 448, 97−103. Choquesillo-Lazarte, D.; Ben Salah, A.; Viñas, C.; Núñez, R. (57) Soldevila-Sanmartín, J.; Ruiz, E.; Choquesillo-Lazarte, D.; Photoluminescence in M-Carborane−Anthracene Triads: A Com- Light, M. E.; Viñas, C.; Teixidor, F.; Núñez, R.; Pons, J.; Planas, J. G. bined Experimental and Computational Study. J. Mater. Chem. C Tuning the Architectures and Luminescence Properties of Cu(I) 2018, 6, 11336−11347. Compounds of Phenyl and Carboranyl Pyrazoles: The Impact of 2D (71) Ferrer-Ugalde, A.; Cabrera-González, J.; Juárez-Pérez, E. J.; versus 3D Aromatic Moieties in the Ligand Backbone. J. Mater. Chem. Teixidor, F.; Pérez-Inestrosa, E.; Montenegro, J. M.; Sillanpää, R.; C 2021, 9, 7643−7657. Haukka, M.; Núñez, R. Carborane−Stilbene Dyads: The Influence of 4806 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article Substituents and Cluster Isomers on Photoluminescence Properties. ing via a Series of Ln-MOFs with a π-Conjugated and Uncoordinated Dalton Trans. 2017, 46, 2091−2104. Lewis Basic Triazolyl Ligand. Inorg. Chem. Front. 2021, 8, 329−338. (72) Cabrera-González, J.; Viñas, C.; Haukka, M.; Bhattacharyya, S.; (90) Lustig, W. P.; Li, J. Luminescent Metal−Organic Frameworks Gierschner, J.; Núñez, R. Photoluminescence in Carborane−Stilbene and Coordination Polymers as Alternative Phosphors for Energy Triads: A Structural, Spectroscopic, and Computational Study. Chem. Efficient Lighting Devices. Coord. Chem. Rev. 2018, 373, 116−147. - Eur. J. 2016, 22, 13588−13598. (91) Mohapatra, S.; Adhikari, S.; Riju, H.; Maji, T. K. Terbium(III), (73) Ferrer-Ugalde, A.; González-Campo, A.; Viñas, C.; Rodríguez- Europium(III), and Mixed Terbium(III)−Europium(III) Mucicate Romero, J.; Santillan, R.; Farfán, N.; Sillanpää, R.; Sousa-Pedrares, A.; Frameworks: Hydrophilicity and Stoichiometry-Dependent Color Núñ ez, R.; Teixidor, F. Fluorescence of New O-Carborane Tunability. Inorg. Chem. 2012, 51, 4891−4893. Compounds with Different Fluorophores: Can It Be Tuned? Chem. (92) Chen, D.-H.; Haldar, R.; Neumeier, B. L.; Fu, Z.-H.; Feldmann, - Eur. J. 2014, 20, 9940−9951. C.; Wöll, C.; Redel, E. Tunable Emission in Heteroepitaxial Ln- (74) Ferrer-Ugalde, A.; Juárez-Pérez, E. J.; Teixidor, F.; Viñas, C.; SURMOFs. Adv. Funct. Mater. 2019, 29, No. 1903086. Sillanpää, R.; Pérez-Inestrosa, E.; Núñez, R. Synthesis and Character- (93) Zhang, J.-C.; Pan, C.; Zhu, Y.-F.; Zhao, L.-Z.; He, H.-W.; Liu, ization of New Fluorescent Styrene-Containing Carborane Deriva- X.; Qiu, J. Achieving Thermo-Mechano-Opto-Responsive Bitemporal tives: The Singular Quenching Role of a Phenyl Substituent. Chem. - Colorful Luminescence via Multiplexing of Dual Lanthanides in Eur. J. 2012, 18, 544−553. Piezoelectric Particles and Its Multidimensional Anticounterfeiting. (75) Lerouge, F.; Viñas, C.; Teixidor, F.; Núñez, R.; Abreu, A.; Adv. Mater. 2018, 30, No. 1804644. Xochitiotzi, E.; Santillan, R.; Farfán, N. High Boron Content (94) Pan, M.; Zhu, Y.-X.; Wu, K.; Chen, L.; Hou, Y.-J.; Yin, S.-Y.; Carboranyl-Functionalized Aryl Ether Derivatives Displaying Photo- Wang, H.-P.; Fan, Y.-N.; Su, C.-Y. Epitaxial Growth of Hetero-Ln- luminescent Properties. Dalton Trans. 2007, 19, 1898−1903. MOF Hierarchical Single Crystals for Domain- and Orientation- (76) Núñez, R.; Romero, I.; Teixidor, F.; Viñas, C. Icosahedral Controlled Multicolor Luminescence 3D Coding Capability. Angew. Boron Clusters: A Perfect Tool for the Enhancement of Polymer Chem., Int. Ed. 2017, 56, 14582−14586. Features. Chem. Soc. Rev. 2016, 45, 5147−5173. (95) Zhao, Y.-W.; Zhang, F.-Q.; Zhang, X.-M. Single Component (77) Hosmane, N. S. Boron Science: New Technologies and Lanthanide Hybrids Based on Metal−Organic Framework for Near- Applications; CRC Press, 2016. Ultraviolet White Light LED. ACS Appl. Mater. Interfaces 2016, 8, (78) Dash, B. P.; Satapathy, R.; Maguire, J. A.; Hosmane, N. S. 24123−24130. Polyhedral Boron Clusters in Materials Science. New J. Chem. 2011, (96) Ramya, A. R.; Sharma, D.; Natarajan, S.; Reddy, M. L. P. Highly 35, 1955−1972. Luminescent and Thermally Stable Lanthanide Coordination (79) Mukherjee, S.; Thilagar, P. Boron Clusters in Luminescent Polymers Designed from 4-(Dipyridin-2-Yl)Aminobenzoate: Efficient Materials. Chem. Commun. 2016, 52, 1070−1093. Energy Transfer from Tb3+ to Eu3+ in a Mixed Lanthanide (80) Zhang, H.; Li, W.; Yan, X.; Cai, W.; Li, M.; He, R.; Shen, W. Coordination Compound. Inorg. Chem. 2012, 51, 8818−8826. Electronic Structure and Luminescence Properties of Unique (97) Im, W. B.; Brinkley, S.; Hu, J.; Mikhailovsky, A.; DenBaars, S. Complexes: Cyclometalated Iridium(III) Chelated by: O-Carbor- P.; Seshadri, R. Sr2.975−xBaxCe0.025AlO4F: A Highly Efficient anyl-Pyridine Ligands. New J. Chem. 2018, 42, 5955−5966. Green-Emitting Oxyfluoride Phosphor for Solid State White Lighting. (81) Xu, W.-J.; Qin, Y.-Y.; Wei, L.-W.; Zhang, K. Y.; Liu, S.-J.; Zhao, Chem. Mater. 2010, 22, 2842−2849. Q. Boron-Functionalized Phosphorescent Iridium(III) Complexes. (98) Ou, Y.; Zhou, W.; Zhu, Z.; Ma, F.; Zhou, R.; Su, F.; Zheng, L.; Eur. J. Inorg. Chem. 2017, 2017, 4393−4405. (82) Xia, Q.; Zhang, J.; Chen, X.; Cheng, C.; Chu, D.; Tang, X.; Li, Ma, L.; Liang, H. Host Differential Sensitization toward Color/ H.; Cui, Y. Synthesis, Structure and Property of Boron-Based Metal− Lifetime-Tuned Lanthanide Coordination Polymers for Optical Organic Materials. Coord. Chem. Rev. 2021, 435, No. 213783. Multiplexing. Angew. Chem., Int. Ed. 2020, 59, 23810−23816. (83) Wang, J.-J.; Si, P.-P.; Liu, M.-J.; Chen, Y.; Yu, S.-X.; Lu, M.; (99) Xie, Y.; Arno, M. C.; Husband, J. T.; Torrent-Sucarrat, M.; Wang, S.-Y.; Li, B.; Li, P.-P.; Zhang, R.-C. Selective Fluorescent O’Reilly, R. K. Manipulating the Fluorescence Lifetime at the Sub- Sensing and Photodegradation Properties of Tb(III)-Based MOFs Cellular Scale via Photo-Switchable Barcoding. Nat. Commun. 2020, with Different Bulky Backbone Ligands. Polyhedron 2019, 157, 63− 11, No. 2460. 70. (100) Deneff, J. I.; Butler, K. S.; Rohwer, L. E. S.; Pearce, C. J.; (84) Sun, M.-L.; Zhang, J.; Lin, Q.-P.; Yin, P.-X.; Yao, Y.-G. Valdez, N. R.; Rodriguez, M. A.; Luk, T. S.; Sava Gallis, D. F. Multifunctional Homochiral Lanthanide Camphorates with Mixed Encoding Multilayer Complexity in Anti-Counterfeiting Heterome- Achiral Terephthalate Ligands. Inorg. Chem. 2010, 49, 9257−9264. tallic MOF-Based Optical Tags. Angew. Chem., Int. Ed. 2021, 60, (85) Zhao, Z.-P.; Zheng, K.; Li, H.-R.; Zeng, C.-H.; Zhong, S.; Ng, S. 1203−1211. W.; Zheng, Y.; Chen, Y. Structure Variation and Luminescence of 3D, (101) Fox, M. A. Icosahedral Carborane Derivatives. Ph.D.Thesis, 2D and 1D Lanthanide Coordination Polymers with 1,3-Adamanta- Durham University, 1991. nediacetic Acid. Inorg. Chim. Acta 2018, 482, 340−346. (102) Sheldrick, G. M. SHELXT-Integrated Space-Group and (86) Li, Y.; Wang, N.; Xiong, Y.-J.; Cheng, Q.; Fang, J.-F.; Zhu, F.-F.; Crystal-Structure Determination. Acta Crystallogr., Sect. A: Found. Long, Y.; Yue, S.-T. Lanthanide Metal−Organic Frameworks Based Adv. 2015, 71, 3−8. on the 4,4′-Oxybisbenzoic Acid Ligand: Synthesis, Structures and (103) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. Physical Properties. New J. Chem. 2015, 39, 9872−9878. K.; Puschmann, H. OLEX2: A Complete Structure Solution, (87) Cui, Y.; Zhang, J.; Chen, B.; Qian, G. Chapter 290 - Lanthanide Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42, Metal-Organic Frameworks for Luminescent Applications. In 339−341. Including Actinides, Bünzli, J.-C. G.; Pecharsky, V. K., Eds.; Handbook (104) Sheldrick, G. M. Crystal Structure Refinement with SHELXL. on the Physics and Chemistry of Rare Earths; 2016; Vol. 50, pp 243− Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3−8. 268. (105) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; (88) de Lill, D. T.; de Bettencourt-Dias, A.; Cahill, C. L. Exploring Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Lanthanide Luminescence in Metal-Organic Frameworks: Synthesis, Jr.; Stratmann, R. E.; Burant, J. C. et al., Gaussian 16, Rev. C.01, Structure, and Guest-Sensitized Luminescence of a Mixed Europium/ Gaussian, Inc.: Wallingford, CT, 2016. Terbium-Adipate Framework and a Terbium-Adipate Framework. (106) Becke, A. D. Density-Functional Thermochemistry .3. The Inorg. Chem. 2007, 46, 3960−3965. Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648−5652. (89) Ma, L.-L.; Yang, G.-P.; Li, G.-P.; Zhang, P.-F.; Jin, J.; Wang, Y.; (107) Perdew, J. P.; Ernzerhof, M.; Burke, K. Rationale for mixing Wang, J.-M.; Wang, Y.-Y. Luminescence Modulation, near White exact exchange with density functional approximations. J. Chem. Phys. Light Emission, Selective Luminescence Sensing, and Anticounterfeit- 1996, 105, 9982−9985. 4807 https://doi.org/10.1021/acs.chemmater.2c00323 Chem. Mater. 2022, 34, 4795−4808 Chemistry of Materials pubs.acs.org/cm Article (108) Vydrov, O. A.; Scuseria, G. E. Assessment of a long-range corrected hybrid functional. J. Chem. Phys. 2006, 125, 234109. 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