pubs.acs.org/crystal Article Amide-Driven Secondary Building Unit Structural Transformations between Zn(II) Coordination Polymers Daniel Ejarque, Teresa Calvet, Merce ̀ Font-Bardia, and Josefina Pons* Cite This: Cryst. Growth Des. 2022, 22, 5012−5026 Read Online ACCESS Metrics & More Article Recommendations * sı Supporting Information See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. ABSTRACT: The behavior of coordination polymers (CPs) against external stimuli has witnessed remarkable attention, especially when the resulting CPs present reversible molecular arrays. Accordingly, CPs with these characteristics can lead to Downloaded via 158.109.59.105 on September 27, 2022 at 13:42:38 (UTC). differences in their properties owing to these structural differences, being promising for their use as potential molecular switches with diverse applications. Herein, we have synthesized four Zn(II) CPs bearing α-acetamidocinnamic acid (HACA) and 4,4′-bipyridine (4,4′-bipy). The reaction between Zn(OAc)2·2H2O, HACA, and 4,4′-bipy yields {[Zn(ACA)2(4,4′-bipy)]·EtOH}n (1), which was used for the formation of three CPs through dissolution− recrystallization structural transformations (DRSTs): {[Zn- (ACA)2(4,4′-bipy)]·2MeOH}n (2), {[Zn2 (μ-ACA)2(ACA)2(4,4′-bipy)]·2H2O} n (3), and {[Zn 3(μ-ACA)6(4,4′-bipy)]· 0.75CHCl3}n (4). The study of the four crystal structures revealed that their secondary building units (SBUs) comprise monomeric, dimeric, and trimeric arrangements linked by 4,4′-bipy ligands. The fundamental role of the utilized solvent and/or temperature, as well as their effect on the orientation of the amide moieties driving the formation of the different SBUs is discussed. Furthermore, the reversibility and interconversion between the four CPs have been assayed. Finally, their solid-state photoluminescence has evinced that the effect of the amide moieties not only predetermine a different SBU but also lead to a different emission in 4 compared with 1−3. ■ INTRODUCTION During the last decades, crystal engineering has arisen as an formations (SSSTs)36 and dissolution−recrystallization struc- tural transformations (DRSTs).37 Both types lead to the interdisciplinary field based on the rationalization of crystalline thermodynamic product in specific synthetic conditions,38 structures from their assemblies.1 Over time, the field has been albeit they drive to the formation of CPs with structural branched into multicomponent solids (cocrystals, salts, and differences. The SSSTs occur in the solid state, which retain solvates)2−4 and coordination polymers (CPs).5−7 In this the main structural integrity of the initial compound. regard, CPs have attracted enormous interest not only for their Differently, in DRSTs, the solvent plays the critical role of structural diversity8−10 but also for their potential applications promoting the dissolution and cleavage of the coordination in gas sorption,11 sensing,12 or catalysis,13 among others.14−16 bonds of the initial compound followed by their rearrangement Their rational design consisting of the judicious selection of into a new complex.39,40 Therefore, SSSTs typically cause metal nodes and organic ligands has led to the formation of the slight structural changes, while DRSTs involve more important desired secondary building units (SBUs), which are directly transformations.41 related with the properties of the resulting compounds.17−19 The coordination, supramolecular interactions, and/or In this context, small changes on the synthetic conditions polarity of the solvent molecules usually lead to DRSTs.42−44 inter alia starting metal salt20 or precursor,21 metal−ligand These differences generally result in changes in the ratio,22 temperature,23 or solvent24 can lead to the obtention of coordination number,45 geometry,40 or dimensionality46 of different CPs. In addition, their possible structural trans- the resulting CPs. Nonetheless, structural transformations of formations triggered by external stimuli (e.g., solvent,25 light,26 heat,27 or synergic effects28,29) have attracted remarkable attention, paving the way for the obtention of new structures Received: May 5, 2022 inaccessible through other synthetic methods.30−32 Besides, Revised: July 1, 2022 when these transformations show a reversible behavior, the Published: July 13, 2022 CPs display promising applications in molecular capture,33 switches,34 and so on.35 Typically, these transformations are sorted into two groups, namely, solid-state structural trans- © 2022 The Authors. Published by American Chemical Society https://doi.org/10.1021/acs.cgd.2c00520 5012 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Scheme 1. Outline of the Formation of Compounds 1−4 the SBUs are relatively scarce,32,47−49 and to the best of our orientations of the acetamide moieties were achieved, and the knowledge, no examples of CPs presenting multiple alterations self-complementary interactions were not always obtained, of its initial SBU by DRSTs can be found in the literature. observing competition with the uncoordinated oxygen atom In this scenario, our group has been working during the last from the carboxylate groups and solvent molecules.51−54 years on the synthesis of CPs based on 4,4′-bipyridine50 and Therefore, aiming to extend our knowledge on ACA-based the preparation of Zn(II) and Cd(II) complexes bearing α- complexes, we have synthesized one CP from the reaction acetamidocinnamic acid (HACA) and different pyridine between Zn(OAc)2·2H2O, HACA, and 4,4′-bipy, namely, derivatives.51−54 These studies resulted in the obtention of a {[Zn(ACA)2(4,4′-bipy)]·EtOH}n (1), which has been used as series of ACA-based compounds with different nuclearities a precursor for DRSTs in different solvents (MeOH, EtOH/ encompassing monomeric, dimeric, trimeric, and even H2O, and CHCl3), yielding three CPs based on variable SBUs, polymeric compounds extended through the ACA ligand. namely, {[Zn(ACA)2(4,4′-bipy)]·2MeOH}n (2), {[Zn2(μ- From them, the obtention of trimeric compounds with ACA) 2 (ACA) 2 (4,4′-bipy)]·2H 2 O} n (3), and {[Zn 3 (μ- pinwheel arrays has especially attracted our attention, studying ACA)6(4,4′-bipy)]·0.75CHCl3}n (4), respectively. Further- the effect of the intramolecular N−H···OC�O synthon between more, the crystal structures of the four compounds have vicinal ACA ligands, which plays an important role in the been elucidated and studied. For 1 and 4, they correspond to stabilization of the SBU.52 This effect led us to study the {[Zn(ACA)2(4,4′-bipy)]·2.5EtOH} n (1C) and {[Zn3(μ- influence of the orientation of the acetamide moieties on their ACA)6(4,4′-bipy)]·8CHCl3}n (4C) (Scheme 1). The effects nuclearity, observing that they tend to form self-complemen- of the solvent in the orientation of the amide moieties driving tary N−H···O interactions that fold inward or outward the the formation of different SBUs have been studied as well as complex depending on the solvent. While in solvents with the interconversion between these CPs. Finally, we further higher H-acceptor propensity such as MeOH or DMF, the analyzed the solid-state photoluminescence of the resulting acetamide moieties fold outward, displaying N−H···Osolvent compounds. interactions, in other solvents with less propensity to partake in H-bonding such CH3CN, the acetamide moieties orientates inward toward the formation of N−H···OC�O intramolecular ■ EXPERIMENTAL SECTION Synthesis of {[Zn(ACA)2(4,4′-bipy)]·EtOH}n (1). An EtOH interactions.55 In addition, when EtOH was used, different solution (15 mL) of Zn(OAc)2·2H2O (100 mg, 0.456 mmol) was 5013 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Table 1. Crystal Data and Structure Refinement for 1C, 2, 3, and 4C 1C 2 3 4C empirical formula C74H86N8O17Zn2 C34H36N4O8Zn C27H26N3O7Zn C84H76Cl24N8O18Zn3 formula weight 1490.24 694.04 569.88 2532.43 T (K) 100(2) 100(2) 100(2) 100(2) wavelength (Å) 0.71073 0.71073 0.71073 0.71073 system, space group triclinic, P1̅ monoclinic, C2/c triclinic, P1̅ triclinic, P1̅ unit cell dimensions a (Å) 9.3672(9) 29.244(2) 9.0797(10) 13.4193(13) b (Å) 13.9712(15) 5.7440(4) 9.4746(10) 14.4425(12) c (Å) 16.0805(18) 19.4053(17) 15.4667(17) 16.0580(16) α (°) 64.504(4) 90 78.255(4) 72.773(4) β (°) 79.901(4) 92.191(3) 85.712(4) 66.418(4) γ (°) 79.650(4) 90 87.664(4) 87.280(4) V (Å3) 1857.2(3) 3257.3(5) 1298.6(2) 2715.3(4) Z 1 4 2 1 Dcalc (mg/m3) 1.332 1.415 1.457 1.549 μ (mm−1) 0.718 0.812 0.997 1.311 F (000) 782 1448 590 1278 crystal size (mm−3) 0.120 × 0.08 × 0.060 0.180 × 0.080 × 0.040 0.250 × 0.200 × 0.100 0.030 × 0.020 × 0.010 hkl ranges −13 ≤ h ≤ 13, −17 ≤ k ≤ 20, −41 ≤ h ≤ 41, −8 ≤ k ≤ 8, −12 ≤ h ≤ 12, −13 ≤ k ≤ 13, −16 ≤ h ≤ 16, −18 ≤ k ≤ 18, 0 ≤ l ≤ 23 −24 ≤ l ≤ 27 −22 ≤ l ≤ 22 −20 ≤ l ≤ 20 θ range (°) 2.224−31.378 2.100−30.605 2.196−30.590 2.051−26.493 reflections collected/ 11,749/11749/0.0587 25,688/5003/0.1150 52,017/7846/0.0272 70,704/11166/0.1653 unique/[Rint] completeness to θ (%) 99.9 99.9 97.7 99.9 absorption correction semi-empirical from semi-empirical from semi-empirical from equivalents semi-empirical from equivalents equivalents equivalents max. and min. 0.7461 and 0.6903 0.7461 and 0.6646 0.7461 and 0.6688 0.7454 and 0.6774 transmission refinement method full-matrix least-squares on |F|2 full-matrix least-squares on |F|2 full-matrix least-squares on |F|2 full-matrix least-squares on |F|2 data/restrains/ 11,749/27/461 5003/0/216 7846/5/351 11,166/0/630 parameters goodness-on-fit on F2 1.078 1.081 1.022 1.022 final R indices R1 = 0.0403, wR2 = 0.0931 R1 = 0.0570, wR2 = 0.1011 R1 = 0.0347, wR2 = 0.0895 R1 = 0.0734, wR2 = 0.1245 [I > 2σ(I)] R indices (all data) R1 = 0.0464, wR2 = 0.0998 R1 = 0.1300, wR2 = 0.1363 R1 = 0.0367, wR2 = 0.0915 R1 = 0.1262, wR2 = 0.1469 extinction coefficient n/a 0.00112(15) n/a n/a largest diff-peak and 1.455 and −0.823 0.818 and −1.013 1.340 and 0.846 1.380 and −1.214 hole (e. Å−3) slowly added to an EtOH solution (15 mL) of HACA (187 mg, 0.911 CHCl3 molecules upon air exposure. Therefore, the dried products mmol) and 4,4′-bipy (285 mg, 1.82 mmol) at RT. The resulting 2−4 were characterized (see the Supporting Information). solution was stirred for 24 h until a white solid precipitated, and then, X-ray Crystallographic Data. For compounds 1C, 2, 3, and 4C, it was kept at −30 °C for 1 h. Then, the solid was filtered, washed colorless prism-like specimens were used for the X-ray crystallo- twice with 10 mL of cold Et2O, and dried under vacuum. During the graphic analysis. For all the compounds, the frames were integrated attempts to obtain single crystals, suitable colorless crystals for X-ray using the Bruker SAINT software package using a narrow-frame diffraction of {[Zn(ACA)2(4,4′-bipy)]·2.5EtOH}n (1C) were ob- algorithm. All hydrogen atoms were refined using a riding model tained. These crystals were obtained using the same molar ratio as for (AFIX) with an isotropic temperature factor equal to 1.2, the 1, but starting from 4.0 mg of Zn(OAc)2·2H2O and using a cooling equivalent temperature factor of the atom to which they are linked, ramp from 50 to 25 °C (SI: Figure S1). When these crystals were and thus, the bond lengths of X−H were fixed. Crystal data and exposed to air, the loss of EtOH molecules yielded 1, which was additional details of structure refinement for compounds 1C, 2, 3, and characterized (details are given in the Supporting Information). 4C are reported in Table 1 and in the Supporting Information. Obtention of 2−4. These compounds were obtained by DRSTs Complete information about the crystal structure and molecular of 1 (20 mg, 0.030 mmol) in MeOH, EtOH/H2O, and CHCl3, geometry is available in the CIF format via CCDC 2168566 (1C), yielding different polymeric arrays with variable SBUs. DRST of 1 in 2168567 (2), 2168568 (3), and 2168569 (4C). MeOH results in the formation of {[Zn(ACA)2(4,4′-bipy)]· 2MeOH}n (2) after keeping the resulting solution in the fridge at 4 °C overnight, while DRST of 1 in EtOH/H2O (18/1) at 70 °C during 12 h at autogenous pressure affords {[Zn 2 (μ- ■ RESULTS AND DISCUSSION Formation of 1−4. Compound 1 was obtained by the ACA)2(ACA)2(4,4′-bipy)]·2H2O}n (3). Finally, when DRST of 1 addition of Zn(OAc)2·2H2O, HACA, and 4,4′-bipy in a 1:2:4 was conducted in CHCl3 at 30 °C during 12 h under autogenous pressure, single crystals of {[Zn3(μ-ACA)6(4,4′-bipy)]·8CHCl3}n molar ratio, respectively, in EtOH as the solvent at RT. During (4C) were obtained. The crystals of 2, 3, and 4C were collected by the attempts to obtain single crystals suitable for X-ray filtration and dried under vacuum, obtaining {[Zn3(μ-ACA)6(4,4′- diffraction, compound 1C was obtained (details are provided bipy)]·0.75CHCl3}n (4) from compound 4C, which unavoidably lost in the Supporting Information). 5014 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Figure 1. Molecular structure of compounds (a) 1C and (b) 2. The recrystallization of 1 in different solvents resulted in the Therefore, the TG-DTA measurements agree with the PXRD formation of CPs consisting of variable SBUs linked by 4,4′- and EA results. The positive ionization mass spectra (ESI+- bipy ligands. Its DRST in MeOH afforded 2 based on MS) of all the compounds were recorded using MeOH as the monomeric SBUs. When 1 was dissolved in EtOH/H2O (18/ solvent. In these conditions, all the CPs show the peaks of the 1) at 70 °C, compound 3 consisting of dimeric SBUs was free ligands at m/z 157.0762 (100%) [4,4′-bipy + H]+ and obtained, while the dissolution of 1 in CHCl3 at 30 °C resulted 228.0622 (100%) [HACA + Na]+ as well as Zn fragments with in the formation of 4C based on trinuclear pinwheel arrays, monomeric, dimeric, and trimeric patterns at m/z 473.0697 which unavoidably lose CHCl3 molecules upon exposure to air, (100%) [Zn(ACA)2 + H]+, 495.0492 (100%) [Zn(ACA)2 + forming 4. Because 2 and 4 are obtained through the direct Na]+, 740.0591 (79%) [Zn2(ACA)3]+, 967.1126 (74%) DRSTs of 1 in MeOH and CHCl3, the solvent plays a crucial [Zn2(ACA)4 + Na]+, and 504.0268 (40%) [Zn3(ACA)4]2+ role in their transformations. Otherwise, the formation of 3 (SI: Figure S8). also need to achieve a temperature of 70 °C for conducting the In the FTIR-ATR spectra, the absence of bands between DRST of 1 in the specified EtOH/H2O ratios and therefore, 2704−2405 cm−1 corresponding to ν(O−H)HACA, combined the synergistic effects of temperature and solvents are the with a strong peak at 1637 cm−1 attributable to ν- driving forces that lead the structural transformation. In (COOH)HACA, indicates that the HACA is deprotonated in addition, the reaction of 1 in the absence of the solvent until the four CPs. The spectra display the typical bands between temperatures of 90 °C or by mechanochemical grinding was 1608−1523 cm−1 for νas(COO) and 1410−1372 cm−1 for also performed to ascertain that no SSSTs occur, obtaining the νs(COO). The difference between these bands [Δ = initial compound. Alternatively, compound 2 has also been νas(COO) - νs(COO)] is 236 cm−1 (1), 207 cm−1 (2), 175 obtained through the direct reaction between Zn(OAc)2· and 113 cm−1 (3), and 184 cm−1 (4), suggesting monodentate 2H2O, HACA, and 4,4′-bipy in a 1:2:4 molar ratio in MeOH, (1 and 2), bidentate chelate (3), and bidentate bridged (3 and while all the attempts to obtain 3 and 4 directly from the 4) coordination modes of the carboxylate groups.57,58 starting reagents were not successful. Moreover, additional groups of the ACA ligand such as the General Characterization. Compounds 1−4 were char- acterized by powder X-ray diffraction (PXRD), HR-ESI-MS, NH and C�O groups have also been identified in all of the elemental analysis (EA), FTIR-ATR, 1H, 13C{1H}, and DEPT- spectra, as well as the ν(C−H)ar, ν(C�C/C�N), δip(C−H), 135 NMR spectroscopies, and single crystal X-ray diffraction and δoop(C−H) bands from the aromatic rings.59 The presence method (1C, 2, 3 and 4C). Furthermore, the thermal stability of solvent molecules allows further identification of some of 1 and 4 was studied via TG-DTA determinations. Phase specific bands in 1−3, observing different peaks at 3455−3378 purity of the bulk samples of 1−4 was verified by PXRD. cm−1 (1), 3646 cm−1 (2), and 3581 and 3496 cm−1 (3) Compounds 2 and 3 are stable under air exposure, while 1 and attributable to ν(O−H) (SI: Figures S9−S12). 4 lose solvent molecules upon exposure to air, resulting in a The 1H NMR spectra of 1−4 were recorded in DMSO-d6 different packing of the crystal structures (1C and 4C) solutions to distinguish between the different molar ratios of compared with the powder (1 and 4) (SI: Figures S2−S5).56 the ligands (ACA:4,4′-bipy) (SI: Figures S13−S16). The EA of 2 and 3 agree with the proposed formula, while in 1C spectra of the four complexes show a signal between 9.20 and and 4C, a loss of solvent that is consistent with the PXRD data 9.17 ppm attributable to the amide proton atom of ACA, while is observed. Considering the differences between 1/1C and 4/ the signals of the aromatic protons of 4,4′-bipy and ACA 4C in the PXRD and EA, TG-DTA determinations of the solid appear between 8.73−7.83 and 7.50−7.28 ppm, respectively. samples of 1 and 4 were performed to verify the loss of solvent Moreover, a signal at 7.24−7.23 ppm corresponding to the molecules and stability of these CPs. For 1, a loss of one EtOH alkene proton is also observed. Finally, the methyl protons molecule (exp. 4.88%; calc. 6.81%) between 40 and 202 °C appeared at 1.96−1.95 ppm. The 1H NMR spectra of 1−4 was observed, followed by its decomposition at 232 °C (SI: confirm the different ACA:4,4′-bipy ratios of the CPs, being Figure S6). For 4, any mass loss was observed until its 2:1 (1 and 2), 4:1 (3), and 6:1 (4), which is in line with the decomposition, being stable until 244 °C (SI: Figure S7). data from the X-ray crystallographic analysis.59 5015 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Table 2. Selected Bond Lengths (Å), Bond Angles (°), and Intermolecular Interactions (Å) for 1C bond lengths (Å) Zn(1)-O(1) 1.9211(11) Zn(1)-N(3) 2.0268(13) Zn(1)-O(4) 2.0093(11) Zn(1)-N(4) 2.0666(13) bond angles (°) O(1)-Zn(1)-O(4) 111.79(5) O(4)-Zn(1)-N(3) 107.52(5) O(1)-Zn(1)-N(3) 129.27(5) O(4)-Zn(1)-N(4) 97.94(5) O(1)-Zn(1)-N(4) 105.23(5) N(3)-Zn(1)-N(4) 99.65(6) intermolecular interactions (Å) D-H···A D-H (Å) H···A (Å) D···A (Å) >D-H···A (°) N(1)-H(1)···O(6) 0.88 2.02 2.829(2) 153 N(2)-H(2)···O(3) 0.88 1.99 2.837(2) 160 C(4)-H(4A)···O(6) 0.98 2.49 3.319(2) 142 C(15)-H(15A)···O(3) 0.98 2.33 3.156(2) 142 C(28)-H(28)···O(1W) 0.95 2.59 3.464(3) 154 O(2W)-H(2WO)···O(2) 0.84 1.92 2.727(3) 160 C(2W)-H(2WC)···O(5) 0.98 2.53 3.360(5) 142 C(10)-H(10)···O(3W) 0.95 2.79 3.578(7) 141 C(27)-H(27)···O(2) 0.95 2.45 3.238(3) 140 C(4)-H(4B)···O(4) 0.98 2.55 3.409(2) 147 Table 3. Selected Bond Lengths (Å), Bond Angles (°), and Intermolecular Interactions (Å) for 2a bond lengths (Å) Zn(1)-O(1) 1.965(2) Zn(1)-N(2) 2.022(2) Bond angles (°) O(1)-Zn(1)-O(1)#1 100.30(13) O(1)-Zn(1)-N(2)#1 104.45(10) O(1)-Zn(1)-N(2) 114.90(10) N(2)-Zn(1)-N(2)#1 116.89(14) intermolecular interactions (Å) D-H···A D-H (Å) H···A (Å) D···A (Å) >D-H···A (°) N(1)-H(1)···O(2) 0.88 2.04 2.813(3) 146 C(15)-H(15)···O(1) 0.95 2.33 3.167(4) 147 O(1W)-H(1WO)···O(3) 0.84 2.00 2.762(4) 151 C(13)-H(13)···O(1W) 0.95 2.42 3.150(5) 134 a #1: x + 1, y, −z + 3/2. The 13C{1H} and DEPT-135 NMR spectra of 1−4 have also in voids generated by the supramolecular scaffold with an been recorded in DMSO-d6 solutions (SI: Figures S17−S20). accessible volume of 181.11 Å3 (9.8% of the unit cell volume). The spectra of the four complexes display the band assignable For 2, the supramolecular scaffold generates voids with an to the carbon atom of the carbonyl group at 170.6−170.3 ppm, accessible volume of 30.78 Å3 (0.9% of the unit cell volume),62 while the carbon atom from the carboxylate group appears which contain two MeOH molecules. The bond lengths and between 168.7−168.4 ppm. The carbon atoms from 4,4′-bipy bond angles for both CPs oscillate between 1.9211(11)-2.0666 are also observed between 150.7−121.4 ppm. In this region, (13) Å and 97.94(5)-129.27 (5)° (1C), and 1.965(2)-2.022 the two carbon atoms from the double bond of ACA are also (2) Å and 100.30(13)-116.89 (14)° (2), presenting similar observed at 135.2−135.1 and 128.4−128.2 ppm. Additionally, values than other Zn(II) four-coordinated CPs based on the aromatic carbon atoms from ACA are located between monomeric SBUs linked by 4,4′-bipy spacers (Tables 2 and 129.8 and 128.3 ppm. Finally, the methyl carbon atoms from 3).63−65 ACA are found to be at 23.1−23.0 ppm. The intermolecular interactions of 1C and 2 are based on Structural Description of {[Zn(ACA)2(4,4′-bipy)]· the N−H···OC�O (1C) and N−H···OCOO (2) synthons, both 2.5EtOH}n (1C) and {[Zn(ACA)2(4,4′-bipy)]·2MeOH}n (2). supported by C−H···O interactions involving the methyl Compounds 1C and 2 belong to the triclinic P1̅ and groups from ACA and the coordinated carboxylate oxygen monoclinic C2/c space groups, respectively. They consist of atoms and carbonyl oxygen atoms from ACA (1C), or the o-H 1D zig-zag CPs expanded along the [101̅] (1C) and [001] (2) atom from 4,4′-bipy and the coordinated oxygen atoms from directions. These polymers are assembled by monomeric SBUs the carboxylate of ACA (2). These interactions expand the with a [ZnO2N2] (1C and 2) core composed by two structures along the [100] (1C) and [010] (2) directions, monodentate (μ1-η1) ACA ligands as well as one 4,4′-bipy, which in combination with the corresponding 4,4′-bipy which joins together the monomeric SBUs (Figure 1). The expansion form 2D supramolecular layers along the (101) evaluation of the geometry has been done using the low (1C) and (011) (2) planes (Tables 2 and 3; Figure 2a,b). continuous shape measure (CShM) value S.60 Both S values fit Additionally, one pair of EtOH molecules in 1C is joined with a tetrahedral geometry (1C: 0.946; 2: 0.630) (SI: Table together to the polymeric array through O−H···O interactions S1), which consistently agree with the τ4 values (1C: 0.84; 2: with the oxygen atoms from the uncoordinated carboxylate 0.91).61 The unit cell of 1C contains two equivalent polymeric groups, while the other three EtOH molecules present weak chains and five EtOH molecules. These solvent molecules are C−H···O interactions involving the oxygen atoms from 5016 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Figure 2. General views of the intermolecular interactions expanding the structure of (a) 1C through the (101) plane and (b) 2 along the (011) plane. (c) In detail view of the intermolecular interactions of 1C. carboxylate ACA groups, a m-H from ACA, and a o-H from a Otherwise, their intermolecular interactions consist of weak 4,4′-bipy (Figure 2c). By the same token, the MeOH C−H···π associations involving the methyl groups of ACA and molecules of 2 interact with the polymeric chains through a contiguous aromatic rings from nearby ACA ligands, double C−H···O interaction involving a m-H from 4,4′-bipy supporting the supramolecular expansion. All this set of and a H-bond between the MeOH and the oxygen atom from interactions expand the structure of 3 along the a axis, which in the carbonyl moieties of ACA. (Figure 2b). combination with the molecular propagation of the CP forms Structural Description of {[Zn2(μ-ACA)2(ACA)2(4,4′- 2D layers along the (110) plane (Figure 3c). bipy)]·2H2O}n (3). Compound 3 belongs to the triclinic P1̅ Structural Description of {[Zn3(μ-ACA)6(4,4′-bipy)]· space group. It consists of a zig-zag CP expanded along the 8CHCl3}n (4C). Compound 4C belongs to the triclinic P1̅ [11̅0] direction. The CP is formed by dimeric SBUs with a space group. It consists of a linear CP formed by pinwheel [ZnO4N] core composed by one bridging (μ2-η1:η1) and one arrays connected through 4,4′-bipy ligands along the [011̅] chelate (μ1-η2) ACA, as well as one 4,4′-bipy ligands, all of direction. The ACA ligands display six μ2-η1:η1 coordination them displaying a distorted square pyramidal geometry (S = modes, which form the pinwheel SBU, accommodating 2.525) (Figure 3a; SI: Table S1). Furthermore, its τ5 value of tetrahedral geometries in the lateral Zn(II) cores (S = 0.843, 0.30 also agrees with a square pyramidal geometry presenting τ4 = 0.93),61 and an octahedral geometry for the central Zn(II) an important distortion.66 Additionally, the supramolecular atom (S = 0.245, ata = 60°)70,71 (Figure 4a; SI: Table S1). In array of 3 generates voids with an accessible volume of 3.10 Å3 addition, the supramolecular scaffold of 4C generates voids (0.2% of the unit cell volume),62 where two water molecules with an accessible volume of 406.46 Å3 (15.0% of the unit cell are located. The bond lengths and bond angles oscillate volume),62 containing eight CHCl3 molecules. The bond between 1.9739(11)-2.0750 (13) Å and 61.32(5)-153.20 (5)° lengths and bond angles oscillate between 1.926(4)-2.096 (4) (Table 4), presenting similar values than other Zn(II) CPs Å and 85.08(14)-180° (Table 5), presenting similar values containing dimeric SBUs formed by carboxylate ligands and than other Zn(II) CPs bearing pinwheel arrays and 4,4′- 4,4′-bipyridines as spacers.67−69 bipyridine ligands as spacers.52,72,73 The intramolecular interactions of 3 are based on one N− The intramolecular interactions of 4C consist of a hexagonal H···OC�O synthon between contiguous ACA units, which in pattern of contiguous N−H···OC�O synthons that stabilize the combination with a Ow−Hw···OC�O interaction involving the pinwheel array (Figure 4b). By the other side, its water molecules support the dimeric array (Figure 3b). intermolecular interactions show that six CHCl3 molecules 5017 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Figure 3. (a) Molecular structure of compound 3. (b) Intra- and intermolecular interactions involving the amide moieties of ACA. (c) Supramolecular expansion of 3 along the (110) plane. Table 4. Selected Bond Lengths (Å), Bond Angles (°), and Intra- and Intermolecular Interactions (Å) for 3a bond lengths (Å) Zn(1)-O(1) 2.2373 (11) Zn(1)-O(5)#1 1.9755(11) Zn(1)-O(2) 2.0642(11) Zn(1)-N(3) 2.0750(13) Zn(1)-O(4) 1.9739(11) bond angles (°) O(1)-Zn(1)-O(2) 61.32(5) O(2)-Zn(1)-O(5)#1 113.45(5) O(1)-Zn(1)-O(4) 95.34(4) O(2)-Zn(1)-N(3) 97.29(5) O(1)-Zn(1)-O(5)#1 108.08(5) O(4)-Zn(1)-O(5)#1 110.13(4) O(1)-Zn(1)-N(3) 153.20(5) O(4)-Zn(1)-N(3) 89.28(5) O(2)-Zn(1)-O(4) 135.08(5) O(5)#1-Zn(1)-N(3) 94.91(5) intramolecular interactions (Å) D-H···A D-H (Å) H···A (Å) D···A (Å) >D-H···A (°) N(2)-H(2)···O(3) 0.88 1.95 2.8079(16) 166 intermolecular interactions (Å) D-H···A D-H (Å) H···A (Å) D···A (Å) >D-H···A (°) N(1)-H(1)···O(6) 0.88 2.04 2.8901(17) 161 O(1W)-H(1WA)···O(6) 0.83(3) 2.12(3) 2.900(3) 158(4) C(22)-H(22C)···Cg(1) 0.98 2.93 3.7856(17) 146 a #1: −x + 1, −y + 1, −z + 1. Cg(1) = C(4) C(5) C(6) C(7) C(8) C(9). are placed around the polymeric chains occupying all the supramolecular interactions combined with the propagation carbonyl oxygen atoms from the ACA ligands forming C−H··· of the CP form a 3D net. O interactions. In addition, two CHCl3 molecules are joined Solvent Controlled SBU Formation. The intricated together to nearby CHCl3, displaying quasi-type I halogen energetic landscape of CPs allows the obtention of different bond interactions (|θ1 − θ2| = 15.53°) (Figure 4b).74 Because molecular arrays with subtle energetic differences that can be the strong H-bonds partake in the intramolecular stabilization overcome by supramolecular interactions (e.g., H-bonds or of the SBU and the interactions with the solvent molecules, the planar interactions), guiding toward specific assemblies.75 For supramolecular expansion of the chain is performed by three accomplishing that, hydrogen bonding has been used as an weak C−H···π interactions between ACA and 4,4′-bipy ligands important structure-directing agent for the obtention of CPs. and ACA ligands by itself expanding the structure along the In this context, the role of amide-based linkers driving the (002) and (110) planes (Figure 4c,d). All this set of formation of different CPs has been widely reported, yielding 5018 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Figure 4. (a) Molecular structure of compound 4C. (b) Intra- and intermolecular interactions involving the amide moieties of ACA. Supramolecular expansions along the (c) (002) and (d) (110) planes. structural transformations based on the reorganization of the with EtOH (Σα = 0.37),55 conjointly with the possibility of the amide groups leading to different linker conformations.76−79 combination of the N−H···OCOO and the MeOH···OCOO However, examples of structural transformations producing interactions to compete with the amide-amide homosyn- changes on the SBU caused by amide groups have been thons,82,83 promoting that the amide moieties fold outward scarce.80 These functional groups tend to form amide-amide from ACA to interact with the MeOH molecules in 2. self-complementary interactions, unless they present geo- For compound 3, the amide moieties display self- metrical restrictions or competing donor/acceptor groups complementary interactions as in 1C, but in this case, the such as solvent molecules, which can disrupt the amide-amide ACA ligands slightly fold inward in pairs toward the formation homosynthons.81 Regarding ACA-based complexes, the strong of intramolecular amide-amide homosynthons. The increase of influence of solvent molecules on the behavior of their amide temperature utilized for reaching 3 from 1 could be an groups has been previously observed by our group, showing important factor that provides enough energy to fold the SBU, that this effect can lead to complexes with different SBUs.51−54 forming an intramolecular pattern that is disrupted by the Herein, the formation of CPs with controlled SBUs depending incorporation of water molecules that replace the position of on the utilized solvents has been discussed. two amide groups. These water molecules can form H-bonds Compounds 1C and 2 present two uncoordinated with interaction energies lying in the same range than the carboxylate oxygen atoms able to competitively disrupt the amide-amide interactions (|Eint| = 35−40 KJ/mol),84 being amide···amide homosynthon. In 1C, the amide moieties able to disrupt the pattern of amide-amide homosynthons, display self-complementary intermolecular interactions and which does not allow additional ACA ligands to partake in the EtOH molecules form additional H-bonds with uncoordi- them, and thus, the trimeric pinwheel array cannot be formed, nated carboxylate oxygen atoms from ACA (Figure 5a). yielding dimeric SBUs (Figure 5c). Otherwise, in compound 2, their two uncoordinated A search in the Cambridge Structural Database (CSD)85 of carboxylate groups interact with the NH of the amide moieties, CPs containing Zn(II) dimeric SBUs with two bridging and while the MeOH molecules are joint to the C�O groups two chelate coordination modes of the carboxylate groups as (Figure 5b). This behavior could be ascribed to the slightly well as pyridine derivatives resulted in 18 hits. This criterion better H-donor propensity of MeOH (Σα = 0.43) compared was applied in order to exclude the most common paddle- 5019 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Table 5. Selected Bond Lengths (Å), Bond and Twist Angles (°), and Intra- and Intermolecular Interactions (Å) for 4C bond lengths (Å) Zn(1)-O(1) 1.941(4) Zn(2)-O(2) 2.065(4) Zn(1)-O(2) 2.065(4) Zn(2)-O(4) 2.089(3) Zn(1)-O(3) 1.926(4) Zn(2)-O(8) 2.096(4) Zn(1)-N(4) 2.046(4) bond angles (°) O(1)-Zn(1)-O(3) 114.35(17) O(2)-Zn(2)-O(4)#1 85.90(15) O(1)-Zn(1)-O(7) 114.80(17) O(2)-Zn(2)-O(8) 92.32(15) O(1)-Zn(1)-N(4) 102.29(17) O(2)-Zn(2)-O(8)#1 87.68(15) O(3)-Zn(1)-O(7) 122.55(17) O(4)-Zn(2)-O(4)#1 180.0 O(3)-Zn(1)-N(4) 97.29(17) O(4)-Zn(2)-O(8) 94.92(14) O(7)-Zn(1)-N(4) 99.58(17) O(4)-Zn(2)-O(8)#1 85.08(14) O(2)-Zn(2)-O(2) #1 180.0 O(8)#1-Zn(2)-O(8) 180.0 O(2)-Zn(2)-O(4) 94.11(15) twist angles (°) O(2)-Cg(1)-Cg(1)-O(8) 61.31 O(8)-Cg(1)-Cg(1)-O(4) 58.66 O(4)-Cg(1)-Cg(1)-O(2) 60.03 intramolecular interactions (Å) D-H···A D-H (Å) H···A (Å) D···A (Å) >D-H···A (°) N(1)-H(1)···O(6) 0.88 2.04 2.811(6) 146 N(2)-H(2)···O(9) 0.88 2.22 2.908(6) 135 N(3)-H(3)···O(5) 0.88 1.99 2.850(7) 166 intermolecular interactions (Å) D-H···A D-H (Å) H···A (Å) D···A (Å) >D-H···A (°) C(39)-H(39)···O(5) 1.00 2.06 3.01(1) 157 C(41)-H(41)···O(6) 1.00 2.06 3.023(7) 161 C(38)-H(38)···Cl(7) 0.95 2.89 3.812(5) 165 C(42)-H(42)···O(9) 1.00 2.16 3.142(9) 167 C(29)-H(29)···Cg(2) 0.95 2.75 3.628(8) 154 C(18)-H(18)···Cg(3) 0.95 2.59 3.431(8) 148 C(7)-H(7)···Cg(4) 0.95 2.83 3.636(8) 143 halogen bonds C-Cl···Cl C-Cl (Å) Cl···Cl (Å) θa (°) C(41)-Cl(8)···Cl(6) 1.722(7) 3.391(3) 152.1(3) C(40)-Cl(6)···Cl(8) 1.732(7) 167.6(3) a θ = C-Cl···Cl angle. Cg(1) = O(2) O(4) O(8); Cg(2) = N(4) C(34) C(35) C(36) C(37) C(38); Cg(3) = C(4) C(5) C(6) C(7) C(8) C(9); Cg(4) = C(26) C(27) C(28) C(29) C(30) C(31). wheel (dimer-4) arrays from the search, which present four space in the coordination sphere. For compound 3, the dimeric bridging coordination modes (Figure 6a).86 From this search, SBU disposition leads to the uncommon distortion from the four different cores have been found, displaying five hits with dimer-2 + 2 supported by amide-amide intramolecular [ZnO4N2], four hits with [ZnO5N], eight hits with [ZnO4N], homosynthons, being in line with the two previous examples and one hit with [ZnO3N] cores. All of the structures containing [ZnO4N] cores.89,90 Thus, the combination of the presenting [ZnO4N2] cores display the dimeric-2 + 2 array amide-amide homosynthon that supports the dimeric SBU (Figure 6b), while the other three types of arrangements are formation, combined with the presence of water molecules that divided into the paddle-wheel and the dimer-2 + 2 disrupt the closing of the round hexagonal pattern of amide- deformations (Figure 6c,d). J.J. Vittal group reported a rare amide intramolecular homosynthons, outstand as two deformation of the paddle-wheel SBU,87 which has been found important factors for the obtention of this uncommon in eight structures (four with [ZnO4N], three with [ZnO5N], distortion of the dimer-2 + 2 SBU in 3 (Figure 6d). and one with [ZnO3N] cores). All of them have been found to Conversely, the recrystallization of 1 in CHCl3 results in the be stabilized by planar intramolecular interactions unless two folding inward of the amide moieties forming a pinwheel array examples where a double intermolecular C−H···O interaction caused by a round hexagonal pattern of amide-amide stabilizes the distortion (Figure 6c). By the other side, the intramolecular homosynthons (4C). Indeed, the presence of distortion from the dimer-2 + 2 has been less reported with CHCl3 as the solvent, which does not compete with the only three examples found in the literature (one with homosynthon formation owing to their poorer H-donor [ZnO5N]88 and two with [ZnO4N]89,90 cores) (Figure 6d). propensity (Σα = 0.15),55 allows to bring together three Zn From them, it has been noticed that both examples showing units completing the round hexagonal pattern of amide-amide [ZnO4N] cores are stabilized by N−H···O intramolecular homosynthons (Figure 5d). interactions such in 3, which promotes a nearing in pairs of the A CSD search of CPs with the pinwheel array containing carboxylate ligands, leading to the cleavage of a pair of pyridine 4,4′-bipyridine ligands reveal a total of 22 hits.85 From them, ligands (one per metal atom) owing to the lack of available five structures are not directed by supramolecular interactions 5020 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Figure 5. Amide behavior in the crystal packing of (a) 1C, (b) 2, (c) 3, and (d) 4C. R1 stands for C7H6 while R2 for C9H6O2. Figure 6. Structure of (a) dimer-4 (paddle-wheel), (b) dimer-2 + 2, (c) deformation from the paddle wheel, and (d) deformation from the dimer-2 + 2. that favor the pinwheel SBU, while 17 structures are stabilized pattern of amide-amide homosynthons arise as an important by round patterns formed by strong H-bonds (seven stabilizing agent for the obtention of pinwheel SBUs. Interconversions between 1−4. The reversibility of the structures) or planar interactions (seven structures), and structural transformations to compound 1, as well as the three structures stabilize the array through weak C−H···O interconversion between 2−4, has been assayed and followed associations. Hence, patterns such as the round hexagonal by PXRD and FTIR-ATR (SI: Figures S2−S5 and S9−S12). 5021 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Scheme 2. Single Crystals of 1/1C-4/4C with an Overview of the Proper Conditions To Achieve the Corresponding Structural Transformations Figure 7. Solid-state emission spectra of compounds 1−4 excited at λexc = 320 nm. The selected colors under the curves of each compound correspond to the observed colors when irradiated at 320 nm according to the CIE 1931 chromaticity diagram. Compounds 2 and 4 can be successfully converted to 1 after the amide moieties of ACA orientate inward or outward, dissolution in EtOH at RT during 12 h. Furthermore, they can driving the formation CPs with specific arrays that are highly be transformed one into another reversibly (2↔4) using the dependent on the solvent (1, 2, and 4) or both the solvent and same synthetic conditions as for the obtention of 2 and 4 from temperature (3). 1 (see the Experimental Section), and both can be Photoluminescence. Photoluminescence properties of 1− interconverted to 3 (2 → 3 and 4 → 3) when the same 4 were recorded using UV excitation of a pulse laser beam at synthetic conditions as for the transformation of 1 → 3 were λexc = 320 nm. Under irradiation, the CPs show unstructured performed (see the Experimental Section). Conversely, emission signals suggesting charge transfer transitions (Figure compound 3 cannot be transformed to neither 1, 2, and 4 7).91 All the emission spectra present one common emission because it does not present enough solubility in MeOH, maxima (λmax‑em) centered at 361 nm with a Stokes shift of EtOH, and CHCl3 to perform the DRSTs (Scheme 2). 3549 cm−1. This band could be assigned to the 4,4′-bipy ligand Therefore, these results show that when dissolution is possible, because it emits in this region when excited at 323 nm.92 5022 https://doi.org/10.1021/acs.cgd.2c00520 Cryst. Growth Des. 2022, 22, 5012−5026 Crystal Growth & Design pubs.acs.org/crystal Article Interestingly, compound 4 presents an additional band at 469 nm with a Stokes shift of 9928 cm−1. It has been noticed that ■ * ASSOCIATED CONTENT sı Supporting Information the presence of Stokes shifts larger than 8000 cm−1 is The Supporting Information is available free of charge at associated with excited-state proton transfers (ESPT).93 These https://pubs.acs.org/doi/10.1021/acs.cgd.2c00520. processes typically take place between atoms involved in strong H-bonds usually bearing -OH functionalities or less commonly Further details of the cooling ramp utilized for the -NHR groups as H-donors, which allow their rational obtention of single crystals of 1C, PXRD diffractograms, functionalization with electron-donor/-withdrawing groups, TG-DTA of 1 and 4, HR-ESI-MS, FTIR-ATR, 1H NMR, 13C{1H} NMR, DEPT-135 NMR spectra of 1−4, resulting in tunable emission wavelengths.94−96 In 4, the as well as relevant data for the geometric evaluations of interaction of the amide moieties is reinforced by the 1C, 2, 3, and 4C cores and photoluminescence properties incorporation of the electron-withdrawing acetyl moieties, of 1−4 (PDF) which increased the acidity of the N−H groups and thus drove the formation of the amide-amide round hexagonal pattern of Accession Codes amide-amide homosynthons. Bearing these factors in mind, CCDC 2168566−2168569 contain the supplementary crys- compound 4 presents the proper structural features, and thus, tallographic data for this paper. These data can be obtained the additional band on their emission spectrum has been free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by ascribed to an ESPT between amides moieties themselves. emailing data_request@ccdc.cam.ac.uk, or by contacting The Otherwise, the arrangement of the amide moieties in 1−3 Cambridge Crystallographic Data Centre, 12 Union Road, seems to not favor the proton transfer between these amide Cambridge CB2 1EZ, UK; fax: +44 1223 336033. groups, which may explain that the band of 469 nm is not present in these CPs. The resultant emission colors for 1−4 under irradiation at 320 nm are aquamarine (1), frosted mind ■ AUTHOR INFORMATION Corresponding Author (2), anakiwa (3), and hot pink (4), in accordance with the CIE Josefina Pons − Departament de Química, Universitat 1931 chromaticity diagrams (Figure 7; SI: Figure S21),97 Autònoma de Barcelona, 08193 Barcelona, Spain; which remarks the difference in color between 1−3 and 4. orcid.org/0000-0003-1834-9326; Email: josefina.pons@ Therefore, the photoluminescence measurements of this series uab.es of CPs, all of them bearing the same former ligands but with different molecular arrays, show how differences on the Authors molecular structure have their effect on the photoluminescence Daniel Ejarque − Departament de Química, Universitat properties, these two factors being directly correlated. Autònoma de Barcelona, 08193 Barcelona, Spain; orcid.org/0000-0002-1014-1128 ■ CONCLUSIONS We have synthesized one CP (1) used as a starting compound Teresa Calvet − Departament de Mineralogia, Petrologia i Geologia Aplicada, Universitat de Barcelona, 08028 Barcelona, Spain; orcid.org/0000-0002-4058-7171 for the obtention of three CPs with variable SBUs (2−4) Mercè Font-Bardia − Unitat de Difracció de Raig-X, Centres through DRST processes. It has been shown that the amide Científics i Tecnològics de la Universitat de Barcelona orientation in the presence of different solvents plays a key role (CCiTUB), Universitat de Barcelona, 08028 Barcelona, on the stabilization of specific SBUs, allowing the obtention of Spain monomeric (1, 2), dimeric (3), or trimeric (4) SBUs Complete contact information is available at: depending on the utilized solvent and/or the temperature. https://pubs.acs.org/10.1021/acs.cgd.2c00520 Interestingly, the presence of water in the DRST of 3 has disrupted the round hexagonal pattern of amide−amide Notes homosynthons driving the formation of an uncommon dimeric The authors declare no competing financial interest. array coming from the deformation of the dimeric-2 + 2 SBU. Furthermore, the round hexagonal pattern of amide−amide homosynthons of 4C has also been shown as a good stabilizing ■ ACKNOWLEDGMENTS J.P. acknowledges financial support from the CB615921 agent for the obtention of pinwheel arrays. Interconversion project, the CB616406 project from “Fundació La Caixa,” assays demonstrate that these transformations are reversible in and the 2017SGR1687 project from the Generalitat de most of the cases, unless for compounds 3, which could be Catalunya. D.E. acknowledges the PIF predoctoral fellowship attributed to its low solubility in MeOH, EtOH, and CHCl3 from the Universitat Autònoma de Barcelona. that do not allow the reorganization of the polymeric array through the corresponding DRST. Finally, solid-state photo- luminescence has been measured observing a different ■ REFERENCES (1) Desiraju, G. R. Crystal Engineering: From Molecule to Crystal. J. behavior of 4 compared with 1−3, which may be attributed Am. Chem. 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