Divergent Structural Transformations in 3D Ag(I) Porous Coordination

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Divergent Structural Transformations in 3D Ag(I) Porous Coordination Polymers Induced by Solvent and Anion Exchanges Cheng-Peng Li, Jin-Yun Ai, Hongming He, Ming-Ze Li, and Miao Du Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01843 • Publication Date (Web): 27 Feb 2019 Downloaded from http://pubs.acs.org on February 27, 2019

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Crystal Growth & Design

Divergent Structural Transformations in 3D Ag(I) Porous Coordination Polymers Induced by Solvent and Anion Exchanges Cheng-Peng Li, Jin-Yun Ai, Hongming He, Ming-Ze Li, and Miao Du*

College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of Inorganic–Organic Hybrid Functional Material Chemistry, Tianjin Normal University, Tianjin 300387, P. R. China

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ACS Paragon Plus Environment

Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT: Two series of ten 3D porous coordination polymers (PCPs), [Ag(L434)](BF4)(DMF)2 (1BF4DMF), [Ag(L434)](BF4)(CH3CN)2 (1BF4CH3CN), [Ag(L434)](BF4)(DMA)(CH3OH) (1BF4DMA/CH3OH), [Ag(L434)](ClO4)(DMF)2 [Ag(L434)](ClO4)(CH3CN)2

(1ClO4DMF), (1ClO4CH3CN),

[Ag(L434)](CF3SO3)(DMF) [Ag(L434)](PF6)(CH3CN)2

(1CF3SO3DMF), (1PF6CH3CN),

[Ag(L434)](CH3SO3)(DMA) (1CH3SO3DMA), [Ag(L434)](CF3SO3)(DMA) (1CF3SO3DMA), and [Ag2(L434)2](BF4)2(CH3OH)2 (2BF4CH3OH), have been prepared via assembling 3,5-bis(4-pyridyl)4-(3-pyridyl)-1,2,4-triazole (L434) with Ag(I) salts in different solvent media. All these PCPs possess 3D porous cationic frameworks, exhibiting irl topology for 2BF4CH3OH and sra topology for others (1anionsolvent) with the same point symbol of (42.63.8). Solvent-induced structural transformations between the topo-isomeric 1BF4solvent and 2BF4CH3OH show drastic deformations of the 3D host frameworks and concomitant solvent exchanges. Three cycles of anion-induced structural conversions involving 1anionDMF, 1anionCH3CN, and 1anionDMA isoreticular structures are also observed, in which the mother frameworks are almost unchanged during the anion exchanges. These two types of structural transformations occur upon different external stimuli (solvent and anion), which are accompanied by significant changes in the shape of channels and the volume of voids.

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INTRODUCTION Recently, porous coordination polymers (PCPs) have been enthusiastically investigated because these molecular-based materials are potentially significant in numerous applications.1–20 For example, robust PCPs tend to be preponderant in high-capacity gas storage; while flexible PCPs can undergo structural changeovers upon guest exchange or removal, resulting in high-selective guest inclusion or recognization.21–30 Structural transformation of PCPs, especially single-crystal-to-single-crystal (SC-SC) transformation,31–33 has been proved to be an appealing pathway to enhance the diversity and functionality of crystalline materials. Notably, the dynamic structural changes generally originate from the synergic effect of atom movement and chemical bonding reorganization. In fact, such behaviors of PCPs invariably caused by different exogenous stimuli, such as concentration, temperature, light and/or mechanical force,34–35 which thus can also be considered as the stimuli-responsive properties of PCPs. SC-SC transformation provides an unequivocal observation of the trace of molecule motion due to the preservation of the single crystalline nature during this process. This feature also facilitates the investigation on structural transformations of PCPs, which currently is an active area of crystal engineering. Herein, we will present two series of ten 3D Ag(I) PCPs with a multiple ligand 3,5-bis(4-pyridyl)-4(3-pyridyl)-1,2,4-triazole

(L434),

including

[Ag(L434)](BF4)(DMF)2

(1BF4DMF),

[Ag(L434)](BF4)(CH3CN)2 (1BF4CH3CN), [Ag(L434)](BF4)(DMA)(CH3OH) (1BF4DMA/CH3OH), [Ag2(L434)2](BF4)2(CH3OH)2 [Ag(L434)](CF3SO3)(DMF)

(2BF4CH3OH), (1CF3SO3DMF),

[Ag(L434)](ClO4)(DMF)2 [Ag(L434)](ClO4)(CH3CN)2

(1ClO4DMF), (1ClO4CH3CN),

[Ag(L434)](PF6)(CH3CN)2 (1PF6CH3CN), [Ag(L434)](CH3SO3)(DMA) (1CH3SO3DMA), and [Ag(L434)](CF3SO3)(DMA) (1CF3SO3DMA), which show multiple guest (solvent or anion) exchanges in the channels and the structural transformations. These reactions can be well confirmed by FT-IR, single crystal X-ray crystallography, and powder X-ray diffraction.

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Scheme 1. Assembling routes of the Ag(I) PCPs in this work.

Experimental Section Materials and Methods. With the exception of the tripyridyl ligand L434, which was prepared according to the literature method,36 all starting reagents and solvents were obtained commercially and used as received. Fourier transform (FT) IR spectra (KBr pellets) were recorded on an AVATAR-370 (Nicolet) spectrometer. Elemental analyses of C, H, and N were performed on a CE-440 (Leemanlabs) analyzer. Thermogravimetric analysis (TGA) plots were carried out on a NETZSCH TG209 (Siemens) thermal analyzer in the temperature range of 25–800 °C at a heating rate of 10 °C/min under nitrogen atmosphere. Powder X-ray diffraction (PXRD) patterns were taken on a Rigaku D/Max-2500 diffractometer at 40 kV and 100 mA for a Cu-target tube ( = 1.5406 Å), with a scan speed of 2 °/min and a step size of 0.02° in 2θ. The calculated PXRD patterns were produced from the single-crystal diffraction data using the PLATON software. Solid-state fluorescent spectra were recorded on a Cary Eclipse spectrofluorimeter (Varian) at room temperature. 4


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Synthesis of [Ag(L434)](BF4)(DMF)2 (1BF4DMF): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) was carefully layered onto a DMF solution (4 mL) of AgBF4 (19.5 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1BF4DMF were obtained by slow evaporation of the solvent at room temperature after two weeks. Anal. Calc. for C23H26AgBF4N8O2: C, 43.08; H, 4.09; N, 17.48%; found: C, 43.26; H, 4.11; N, 17.14%. IR (cm1): 1639s, 1618s, 1555w, 1524w, 1473m, 1435s, 1413m, 1296w, 1218w, 1085vs, 1031s, 994w, 883w, 834m, 708m, 622vs, 482w. Synthesis of [Ag(L434)](BF4)(CH3CN)2 (1BF4CH3CN): A CH3CN solution (4 mL) of AgBF4 (19.5 mg, 0.1 mmol) was carefully layered onto a CHCl3 solution (4 mL) of L434 (30.0 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1BF4CH3CN were obtained by slow evaporation of the solvent at room temperature after one week. Anal. Calc. for C21H18AgBF4N8: C, 43.71; H, 3.14; N, 19.42%; found: C, 43.60; H, 3.29; N, 19.33%. IR (cm1): 2251m, 1610s, 1554m, 1535m, 1484s, 1440s, 1352w, 1284w, 1052vs, 833s, 705s, 663w, 627s, 522w. Synthesis of [Ag(L434)](BF4)(DMA)(CH3OH) (1BF4DMA/CH3OH): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) was carefully layered onto a DMA solution (4 mL) of AgBF4 (19.5 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1BF4DMA/CH3OH were obtained by slow evaporation of the solvent at room temperature after one week. Anal. Calc. for C22H25AgBF4N7O2: C, 43.02; H, 4.10; N, 15.96%; found: C, 43.38; H, 4.19; N, 15.79%. IR (cm1): 3450b, 1637vs, 1608w, 1555w, 1480m, 1434s, 1410m, 1355w, 1265w, 1063vs, 993w, 834m, 729w, 708m, 622m, 593w, 521w, 468w. [Ag2(L434)2](BF4)2(CH3OH)2 (2BF4CH3OH): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) was carefully layered onto a H2O solution (4 mL) of AgBF4 (19.5 mg, 0.1 mmol) in a glass tube, be5



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tween which a buffer solution of acetic ether (2 mL) was added. Pale-yellow block crystals of 2BF4CH3OH were obtained by slow evaporation of the solvent at room temperature after one week. Anal. Calc. for C36H32Ag2B2F8N12O2: C, 41.02; H, 3.06; N, 15.95%; found: C, 41.17; H, 3.09; N, 15.86%. IR (cm1): 3454b, 1608m, 1553w, 1485s, 1438s, 1346w, 1210w, 1197w, 1058vs, 833s, 729w, 707m, 625m, 549w, 523w, 465w. Synthesis of [Ag(L434)](ClO4)(DMF)2 (1ClO4DMF): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) in a glass tube was carefully layered onto a DMF solution (4 mL) of AgClO4 (20.8 mg, 0.1 mmol), between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1ClO4DMF were obtained by slow evaporation of the solvent at room temperature after two weeks. Anal. Calc. for C23H26AgClN8O6: C, 42.25; H, 4.01; N, 17.14%; found: C, 42.42; H, 4.24; N, 17.03%. IR (cm1): 1668s, 1605w, 1482w, 1440m, 1391w, 1256w, 1094vs, 832w, 709w, 661w, 624m, 464w. Synthesis of [Ag(L434)](CF3SO3)(DMF) (1CF3SO3DMF): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) was carefully layered onto a DMF solution (4 mL) of AgSO3CF3 (25.7 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1CF3SO3DMF were obtained by slow evaporation of the solvent at room temperature after one week. Anal. Calc. for C21H19AgF3N7O4S: C, 40.01; H, 3.04; N, 15.55%; found: C, 40.29; H, 3.07; N, 15.34%. IR (cm1): 1669s, 1612m, 1557w, 1533w, 1483m, 1440m, 1413w, 1387m, 1352w, 1269vs, 1222m, 1152vs, 1097vs, 1031m, 1002w, 835s, 748w, 709m, 635s, 544s, 465w. Synthesis of [Ag(L434)](ClO4)(CH3CN)2 (1ClO4CH3CN): A CH3CN solution (4 mL) of AgClO4 (20.8 mg, 0.1 mmol) was carefully layered onto a CHCl3 solution (4 mL) of L434 (30.0 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1ClO4CH3CN were obtained by slow evaporation of the solvent at room temperature after one week. Anal. Calc. for C21H18AgClN8O4: C, 42.77; H, 3.08; N, 19.00%; found: C, 42.85; H, 3.12; N, 6


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18.88%. IR (cm1): 1606m, 1555m, 1522w, 1480m, 1436m, 1334w, 1220w, 1085vs, 993w, 832m, 708m, 623s, 522w, 468w. Synthesis of [Ag(L434)](PF6)(CH3CN)2 (1PF6CH3CN): A CH3CN solution (4 mL) of AgPF6 (25.4 mg, 0.1 mmol) was carefully layered onto a CHCl3 solution (4 mL) of L434 (30.0 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1PF6CH3CN were obtained by slow evaporation of the solvent at room temperature after one week. Anal. Calc. for C21H18AgF6N8P: C, 39.70; H, 2.86; N, 17.64%; found: C, 39.91; H, 2.90; N, 17.42%. IR (cm1): 2251m, 1612s, 1534m, 1486s, 1441s, 1416m, 1376w, 1351w, 1221m, 1198m, 1169w, 1127w, 1104w, 1067m, 1039m, 1010m, 836s, 741s, 705s, 627s, 556s, 466w. Synthesis of [Ag(L434)](CH3SO3)(DMA) (1CH3SO3DMA): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) was carefully layered onto a DMA solution (4 mL) of AgSO3CH3 (20.4 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1CH3SO3DMA were obtained by slow evaporation of the solvent at room temperature after two weeks. Anal. Calc. for C22H24AgN7O4S: C, 44.76; H, 4.10; N, 16.61%; found: C, 44.93; H, 4.13; N, 16.70%. IR (cm1): 1637s, 1536w, 1483m, 1440m, 1416m, 1354w, 1205s, 1059w, 1037m, 1011w, 835m, 757m, 708m, 626m, 591w, 549m, 523m, 469w. Synthesis of [Ag(L434)](CF3SO3)(DMA) (1CF3SO3DMA): A CH3OH solution (4 mL) of L434 (30.0 mg, 0.1 mmol) was carefully layered onto a DMA solution (4 mL) of AgSO3CF3 (25.6 mg, 0.1 mmol) in a glass tube, between which a buffer solution of acetic ether (2 mL) was added. Colorless block crystals of 1CF3SO3DMA were obtained by slow evaporation of the solvent at room temperature after two weeks. Anal. Calc. for C22H21AgF3N7O4S: C, 41.01; H, 3.29; N, 15.22%; found: C, 41.12; H, 3.43; N, 15.01%. IR (cm1): 3062w, 2930w, 1637s, 1534w, 1484m, 1442m, 1418m, 1354w, 1269s, 1223w, 1154s, 1066w, 1030m, 834m, 747m, 708m, 634s, 572w, 516w, 469w. 7



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X-ray Crystallography. Single-crystal X-ray diffraction data for all PCPs were collected on a Bruker Apex II CCD diffractometer at ambient temperature or 173 K with Mo Kα radiation ( = 0.71073 Å). In each case, a semi-empirical absorption correction was applied (SADABS) and the program SAINT was used for integration of the diffraction profiles.37 All structures were solved by direct methods with SHELXS program of the SHELXTL package and refined with SHELXL.38 The non-hydrogen atoms were modelled with anisotropic thermal parameters and refined by full-matrix least-squares methods on F2. In general, C-bound hydrogen atoms were placed geometrically and refined as riding, whereas O-bound hydrogen atoms were firstly located in difference Fourier maps, and then fixed in the calculated sites. As for 1BF4CH3CN and 1BF4DMA/CH3OH, the lattice BF4– anions were treated as the disordered model and assigned to 0.18/0.82 or 0.17/0.83 occupancies to achieve the appropriate thermal parameters. For 1ClO4DMF, the lattice DMF molecule is disordered over two positions with the site occupancy factors of 0.22 and 0.78. With regard to 1CF3SO3DMF, one pyridyl ring (N1) and the lattice DMF molecule are disordered over two positions with the site occupancy factors of 0.38/0.62, the affiliated H atoms of which were thus not located. As for 1ClO4CH3CN, the lattice ClO4– anion was treated as a disordered model with 0.27/0.73 occupancy to achieve the appropriate thermal parameters. Further details for crystallographic data and refinement conditions are listed in Table 1, and selected bond parameters and voids volumes are shown in Table S1 and Table S2, respectively. CCDC1563110 to 1563119 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.

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Table 1. Crystallographic Data and Refinement Conditions.

Compound reference Chemical formula Formula mass Crystal system a/Å b/Å c/Å α/° β/° γ/° Unit cell volume/Å3 Temperature/K Space group No. of formula units per unit cell, Z Absorption coefficient, μ/mm1 No. of reflections measured No. of independent reflections Rint Final R1 values (I > 2σ(I)) Final wR(F2) values (I > 2σ(I)) Final R1 values (all data) Final wR(F2) values (all data) Goodness of fit on F2

1BF4DMF C23H26AgBF4N8O2 641.20 monoclinic 9.196(3) 24.960(9) 14.382(4) 90 122.483(15) 90 2784.7(16) 296(2) P21/c 4 0.786 14148 4915 0.0415 0.0504 0.1206 0.0833 0.1367 1.032

1BF4CH3CN C21H18AgBF4N8 577.11 monoclinic 9.3666(5) 23.7024(13) 12.6894(5) 90 119.236(3) 90 2458.3(2) 173(2) P21/c 4 0.876 13906 4336 0.0197 0.0296 0.0706 0.0309 0.0715 1.054

1BF4DMA/CH3OH C22H25AgBF4N7O2 614.17 orthorhombic 26.090(7) 10.782(3) 9.101(3) 90 90 90 2560.4(13) 173(2) Pna21 4 0.850 13572 4463 0.0256 0.0317 0.0780 0.0335 0.0797 0.973

2BF4CH3OH C36H32Ag2B2F8N12O2 1054.09 orthorhombic 17.655(11) 14.231(8) 16.330(10) 90 90 90 4103(4) 296(2) Pca21 4 1.041 20343 6823 0.0382 0.0404 0.1019 0.0505 0.1083 1.046

1ClO4DMF C23H26AgClN8O6 653.84 monoclinic 9.0456(6) 24.9317(17) 12.1258(9) 90 96.2640(10) 90 2718.3(3) 173(2) P21/n 4 0.893 15575 4791 0.0323 0.0324 0.0806 0.0372 0.0845 0.993

Compound reference Chemical formula Formula mass Crystal system a/Å b/Å c/Å α/° β/° γ/° Unit cell volume/Å3 Temperature/K Space group No. of formula units per unit cell, Z Absorption coefficient, μ/mm1 No. of reflections measured No. of independent reflections Rint Final R1 values (I > 2σ(I)) Final wR(F2) values (I > 2σ(I)) Final R1 values (all data) Final wR(F2) values (all data) Goodness of fit on F2

1CF3SO3DMF C21H19AgF3N7O4S 630.36 orthorhombic 26.9110(16) 10.7270(7) 9.0446(5) 90 90 90 2610.9(3) 173(2) Pna21 4 0.914 14341 4570 0.0333 0.0409 0.0997 0.0423 0.1006 1.057

1ClO4CH3CN C21H18AgClN8O4 589.75 monoclinic 9.3495(12) 23.867(3) 11.4708(15) 90 105.793(2) 90 2463.1(6) 173(2) P21/n 4 0.971 14107 4352 0.0290 0.0279 0.0656 0.0306 0.0677 1.017

1PF6CH3CN C21H18AgF6N8P 635.27 monoclinic 9.3214(15) 23.912(4) 12.064(2) 90 105.218(3) 90 2594.7(7) 296(2) P21/n 4 0.908 13383 4584 0.0237 0.0345 0.0863 0.0427 0.0924 1.024

1CH3SO3DMA C22H24AgN7O4S 590.41 orthorhombic 25.897(4) 11.0500(18) 8.8999(14) 90 90 90 2546.8(7) 173(2) Pna21 4 0.915 13404 4042 0.0461 0.0478 0.1102 0.0588 0.1154 1.079

1CF3SO3DMA C22H21AgF3N7O4S 644.39 orthorhombic 26.4040(13) 11.1833(5) 9.0790(4) 90 90 90 2680.9(2) 296(2) Pna21 4 0.892 13563 4483 0.0327 0.0345 0.0796 0.0465 0.0869 1.023

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RESULTS AND DISCUSSION Structural Description. Single-crystal X-ray diffraction analysis indicates that the series of nine 1anionsolvent coordination polymers exhibit the similar polymeric frameworks with rectangle channels. Thus, only the structure of 1BF4DMF is described herein. 1BF4DMF crystallizes in the P21/c space group and its asymmetric unit comprises one AgI ion, one L434 ligand, one guest BF4– anion, and two lattice DMF molecules. The [AgN4] coordination sphere can be viewed as a distorted tetrahedron, and the four nitrogen donors come from three pyridyl groups and one triazole ring, respectively (Figure 1a). As a result, the adjacent AgI centers are connected by the L434 ligands to form a 3D cationic framework, with 1D rectangle channels along the [100] axis (Figure 1b). Computation of the channel space using PLATON39 reveals a value of 1452.7 Å3 (52.2% per unit cell volume), which is occupied by the BF4– anions and DMF molecules. Topologically, if considering each metal ion and ligand as nodes of the simplified net, then the AgI and L434 tectons can be viewed as the 4-connected nodes with the extended point symbol of [4.6.4.6.62.86], to afford a sra40 net with the point symbol (42.63.8) (Figure 1c).

(a)

10 ACS Paragon Plus Environment

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(b)

(c)

Figure 1. Views of 1·BF4·DMF. (a) Coordination environment of AgI (symmetry codes for A: 1 – x, 2 – y, –z; B: 2 – x, 1/2 + y, 1/2 – z; C: 2 – x, 2 – y, –z). (b) 3D cationic network with the location of lattice DMF solvents and BF4– anions. (c) Topological view of the host framework with sra prototype.

When DMF in 1BF4DMF was exchanged by CH3OH, 2BF4CH3OH can be obtained, which crystallizes in the space group Pca21. The symmetric unit is composed by two crystallographically independent AgI ions, two L434 ligands, two guest BF4– anions, and two lattice CH3OH molecules. In this case, each tetrahedral AgI center coordinates to four separate L434 ligands via three pyridyl groups and one triazole ring (Figure 2a). As a result, the adjacent AgI atoms are connected by the L434 ligands to generate a 3D cationic framework, with 1D hexagonal channels along the [010] axis (Figure 2b). Within each hexagonal channel, three pairs of Ag1 and Ag2 are positioned alternatively, with BF4– anions locating at the center. The voids within this 3D framework are 1260.1 Å3 (30.7% per unit cell volume), which are available for the accommodation of lattice guests. In this network, each AgI and L434 can also be regarded as the 4-connected nodes but with



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the extended point symbol of [4.6.4.6.62.84], constructing an irl net (Figure 2c) which is different to 1BF4DMF although they possess the same point symbol (42.63.8).

(a)

(b)

(c)

Figure 2. Views of 2BF4CH3OH. (a) Coordination environments of AgI (symmetry codes for A: x, 1 + y, z; B: –1/2 + x, 1 – y, z; C: 3/2 – x, –1 + y, 1/2 + z; D: 3/2 – x, y, 1/2 + z; E: 1 – x, –y, 1/2 + z). (b) 3D cationic network with the location of lattice DMF solvents and BF4– anions. (c) Topological view of the host framework with irl prototype. Solvent-Directed Transformations for 1BF4solvent and 2BF4CH3OH: When single crystal sample of 1BF4DMF was immersed into CH3OH solvent at ambient temperature for three days, 12 ACS Paragon Plus Environment

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2BF4CH3OH was produced without the loss of crystallinity. Similar structural transformations were achieved between 1BF4CH3CN or 1BF4DMA/CH3OH and 2BF4CH3OH by changing the solvents (Figure 3a). All these processes can also be accurately traced by PXRD (Figure 3b). Notably, the crystal transformations between 1BF4DMF or 1BF4CH3CN and 2BF4CH3OH are reversible, while that between 1BF4DMA/CH3OH and 2BF4CH3OH is irreversible. This may be caused by the existence of two types of guest solvents in 1BF4DMA/CH3OH and thus, the reversed reaction pathway is difficult to control.



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Figure 3. (a) Schematic views and (b) PXRD plots for solvent-induced transformations between 1BF4solvent and 2BF4CH3OH.

Structural comparison reveals that, some significant divergences exist between 1BF4solvent and 2BF4CH3OH, though they possess the similar coordination geometry of Ag(I) and ligating mode of L434 ligand. First, the shapes of channels are apparently different, changing from rectangle to hexagon. Second, the lattice solvents are distributed in the middle or edge of the channels


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in 1BF4solvent, while in 2BF4CH3OH, all CH3OH molecules are located in the edge. Last, in view of the topology of 3D host networks, although they have the same point symbol of (42.63.8), various extended point symbols of [4.6.4.6.62.86] and [4.6.4.6.62.84] result in the diverse sra and irl topological nets. They both share the opposite edges to form 4-connected patterns via linking the rods of quadrangles, but affording sra or irl net with the rungs parallel or at an angle to each other (Figure 4). Such a topo-isomeric SC-SC transformation is very unusual, which may be due to the labile nature of Ag(I) centers in 1BF4solvent and 2BF4CH3OH. After combination of all these aspects, the transformations between 1BF4solvent and 2BF4CH3OH can be annotated that, upon solvent exchange, some Ag(I) centers rotate in an angle to cause a distortion of the overall network, and both the shape of channel and the framework topology are correspondingly changed. Such SC-SC transformations from 1BF4solvent to 2BF4CH3OH are accompanied by the increment of the unit cell volume up to 47~67% (Table S2). Accordingly, the percentages of void volume for per unit cell decrease from 44~52% in 1BF4solvent to 31% in 2BF4CH3OH. It should be noted that the unit cell content excluding the solvent is doubled from 1BF4solvent to 2BF4CH3OH, so its crystal volume actually decreases, which is in agreement with the decrease of void volume.

Figure 4. Comparison of the topological networks of 1BF4solvent (a) and 2BF4CH3OH (b).



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Solvent Exchanges for 1BF4solvent PCPs: As shown in Figure 3a, reversible transformations are observed between 1BF4DMF and 1BF4CH3CN, whereas irreversible transformations are found from 1BF4DMA/CH3OH to 1BF4DMF or 1BF4CH3CN. All the processes have also been traced by PXRD patterns (Figure 5). For the potential solvent-accessible areas, these three PCPs possess different values with a wide range of 1089~1453 Å3, corresponding to 44.3~52.2% of the unit cell volume (Table S2). The void changes of 1BF4solvent PCPs suggest the soft and flexible nature of host networks and the retention of structures upon solvent exchanges.

Figure 5. PXRD patterns for the solvent exchanges between 1BF4solvent PCPs. 16 ACS Paragon Plus Environment

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Anion Exchanges for 1anionsolvent PCPs: As shown in Figure 6, three transformation cycles have been systematically investigated for reversible anion exchanges. As for 1anionDMF (anion = BF4–, ClO4– or CF3SO3–) and 1anionCH3CN (anion = BF4–, ClO4– or PF6–) PCPs, all these structural transformations are reversible (Figure 6a and 6c), which can be well determined by IR spectra. For example, 1ClO4DMF crystals were chosen as the mother crystals and used in anion-exchanged reactions. Immersion of 1ClO4DMF in a water solution (1 M) of NaSO3CF3 for three days at ambient condition results in a complete exchange of ClO4– by the CF3SO3– anion, without losing morphology and crystallinity of the sample. IR spectra reveal the disappearance of characteristic peak for ClO4– at 1111 cm–1 and the appearance of the strong peak at 1259 cm–1 for CF3SO3– anion (Figure 7). To illustrate the reversibility of anion exchange, the exchanged crystals 1CF3SO3DMF were dipped in a water solution of NaClO4 (1 M) at ambient condition for four days, and the IR spectra clearly show a completely reversible process (Figure S2), in which only the characteristic peak of ClO4– is observed. Similarly, the other anion-exchange reactions of 1anionDMF and 1anionCH3CN PCPs were also accomplished as confirmed by IR spectra. These two series of PCPs have different values of void volume in a wide range of 1100~1453 Å3 and 985~1254 Å3, corresponding to 42.1~52.2% and 40.0~48.3% of the unit cell volume (Table S2), respectively.



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Figure 6. Schematic views of the anion exchanges between 1anionDMF (anion = BF4–, ClO4– or CF3SO3–) (a), 1anionDMA (anion = BF4–, CF3SO3– or CH3SO3–) (b), and 1anionCH3CN (anion = BF4–, ClO4– or PF6–) (c).

Figure 7. IR spectra for anion-exchange from 1ClO4DMF to 1CF3SO3DMF. As for 1anionDMA (anion = BF4–, CF3SO3– or CH3SO3–), reversible anion-exchanges can be achieved between 1CF3SO3DMA and 1CH3SO3DMA (Figure 6b). Starting from the crystal of 1BF4DMA/CH3OH as the parent, anion exchange of BF4– by CF3SO3– or CH3SO3– was availa-


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ble (Figure 6b), while the reversed transformations were unsuccessful that can be ascribed to the existence of mixed guests in 1BF4DMA/CH3OH. For the potential solvent-accessible areas, the three PCPs have different values in a wide range of 1194~1357 Å3, corresponding to 46.9~50.6% of the unit cell volume (Table S2). Thermal Stability: Thermal stability of the PCPs was explored by TGA experiments (see Figure S5 and Table S3). In the similar TGA curves of 1BF4DMF and 1BF4CH3CN, the loss of solvent is firstly observed and then, the residual species suffers a sharp weight loss in 300–400 °C, followed by a slow weight loss until 800 °C. 1BF4DMA/CH3OH shows the weight loss of solvents before 171 °C and a sharp weight loss of framework in 292–400 °C. Then, pyrolysis of the residue is found and does not end till 800 °C. 2BF4CH3OH shows the first weight loss of methanol, and the host framework starts to decompose until 320 °C, which does not stop till 800 °C. For 1CF3SO3DMF, after the release of DMF, a sharp weight loss is found beyond 355 °C, followed by a slow one that does not stop until 800 °C. For 1PF6CH3CN, the first weight loss reveals the elimination of CH3CN. Upon further heating to 368 °C, a sharp weight loss plus a mild one are observed until 800 °C. The TGA curves for 1CH3SO3DMA and 1CF3SO3DMA show the exclusion of lattice DMA. The frameworks is decomposed upon 400 °C, with a sharp weight loss plus a mild one till 800 °C. In order to reveal the role of solvents in these PCPs, PXRD tests of the samples after desorption and resorption of solvents were taken. As shown in Figure S6, all these PCPs will suffer the structural changes after removing the solvent molecules, although their crystallinity will be remained. Notably, only the mother framework of 1BF4 DMA/CH3OH can be recovered after the resorption of solvent. Photoluminescence Properties: Solid-state fluorescent properties of the PCPs mentioned above as well as the L434 ligand were explored at room temperature (Figure S7). The free ligand shows 19 ACS Paragon Plus Environment


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the maximal emission peak at 447 nm (λex = 370 nm), which should be attributed to the π  π* and/or n  π* transitions. Excitation of the microcrystalline samples for PCPs at 370 nm leads to the generation of intense fluorescent emissions, with similar maximum peaks also observed at 447 nm. Obviously, these emissions should be assigned to the ligand-centered transitions. Moreover, the enhancement of their emission intensity at different levels compared with that of ligand can be attributed to the increased rigidity of the L434 ligand when bound to the AgI center, which will effectively prevent the thermal deactivation pathways. CONCLUSION Two series of ten PCPs have shown divergent structural transformations driven by solvent or anion exchanges. In case of solvent exchange reactions between 1BF4solvent and 2BF4CH3OH, the 3D host frameworks distort drastically both in shapes and volumes of the voids, to seek their optimum configurations. Of further interests, topologically, the point symbol of (42.63.8) is maintained, but their network patterns are changed from sra to irl. This can be properly described as the “flexible” nature of these topo-isomeric PCPs. As for the solvent exchange reactions between 1BF4solvent, as well as the three cycles of anion exchanges between 1anionsolvent (solvent = DMF, CH3CN or DMA), their host frameworks only suffer controllable expansion or contraction of porous channels, without the change in net topology. Thus, the framework of 1anionsolvent can be considered as a good platform for various structural transformations, upon different exogenous stimuli, which may be useful to develop dynamic PCPs crystalline materials with potential applications. ASSOCIATED CONTENT Supporting Information


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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ Tables for structural and TGA data as well as PXRD, IR, TGA, and fluorescence plots. AUTHOR INFORMATION Corresponding Author *

E-mail: [email protected]

Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS We are grateful for the support by the National Natural Science Foundation of China (21771139), Tianjin Natural Science Foundation (17JCYBJC22800), the Science & Technology Development Fund of Tianjin Education Commission for Higher Education (2017KJ127), and the Program for Innovative Research Team in University of Tianjin (TD13-5074). REFERENCES (1)

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For Table of Contents Use Only

Divergent Structural Transformations in 3D Ag(I) Porous Coordination Polymers Induced by Solvent and Anion Exchanges Cheng-Peng Li, Jin-Yun Ai, Hongming He, Ming-Ze Li, and Miao Du*

Two series of Ag(I) porous coordination polymers have been constructed, which suffer different cycles of structural transformations driven by solvent and anion exchanges.


Divergent Structural Transformations in 3D Ag(I) Porous Coordination

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