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Mar 22, 2016 - Anion-Mediated Architecture and Photochromism of Rigid ..... (Figure 1c), thus leading to a 3D architecture. ..... 2015, 54, 1756−176...
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Anion-Mediated Architecture and Photochromism of Rigid Bipyridinium-Based Coordination Polymers Jian-Jun Liu,† Ying-Fang Guan,† Mei-Jin Lin,*,†,‡ Chang-Cang Huang,*,† and Wen-Xin Dai† †

College of Chemistry, Fuzhou University, Fuzhou, China, 350116 State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou, China, 350002

‡

S Supporting Information *

ABSTRACT: Four metal−organic coordination compounds Zn2(bcbp)Cl4 (1), Zn(bcbp)(PO3F) (2), [CdCl(Hbcbp)(bcbp)]·(ClO4) 2 (3), and [Cd2(bcbp)4]·(ClO4)·F3 (4) (H2bcbp·2PF6 = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) hexafluorophosphate) have been synthesized via a solvothermal method and structurally characterized. Compound 1 is a 1D coordination polymer, while compound 2 shows a 2D + 2D → 3D inclined polycatenation structure. In the case of compound 3, due to the capped chlorine atoms and uncoordinated carboxyl of bcbp ligand, it exhibits a 1D Tshaped coordination configuration. Compound 4 is an unprecedented 13-fold interpenetrating structure with huge diamondoid frameworks. Because of the presence of electrondeficient bipyridinium moieties, the photochromic behaviors of these compounds have also been studied. Interestingly, only compounds 1−3 exhibit color changes under light irradiation. The impact of these anions on the photochromic process is discussed.

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INTRODUCTION

To the best of our knowledge, only semirigid bipyridinium derivatives have been widely studied,12 while the rigid and linear bipyridinium derivatives and their corresponding coordination polymers in photochromic properties have not been explored. A rigid pyridinium derivative containing conjugated Lewis acid sites, 1,1′-bis(4-carboxyphenyl)-(4,4′bipyridinium) hexafluorophosphate (denoted as H2bcbp·2PF6), is an ideal electron-deficient building blocks for photochromic coordination polymers. Recently we have developed a luminescent material for the sensing of organic amines based on this bipyridinium derivative.11 In order to investigate the effect of different anions on photochromism, here in we report that four metal−organic coordination compounds Zn2(bcbp)Cl4 (1), Zn(bcbp)(PO3F) (2), [CdCl(Hbcbp)(bcbp)]·(ClO4)2 (3), and [Cd2(bcbp)4]·(ClO4)·F3 (4) have been successfully synthesized as well as their crystal structures, and the relationship between the anion and photochromic properties has also been explored.

Photochromic materials as a new class of multifunctional materials have been attracting much attention due to their potential applications in displays, magnetic switching devices, optical data switches, and so on.1 In recent years, the research interest in this area has been focused on constructing new compounds with various functions, such as luminescence, magnetism, electric conductivity, and catalysis.2 The current research exhibits that employment of coordination chemistry is an efficient approach to achieve this purpose.3 Compared with organic ligands, coordination polymers not only show more structural diversity but also possess the synergistic effects between organic and inorganic components.4 Photochromic coordination polymers, if their efficient photochromic species were developed, are regarded to have better properties than traditional photochromic organic dyes.5,6 The most important step to synthesize these materials is to choose suitable acceptors and electron donors.6d,7 4,4′Bipyridinium derivatives are an attractive class of electron acceptors molecules containing an electrically charged moiety in the conjugation, which is the idea electron acceptor for preparing redox photochromic materials.8 Many groups have examined the influence of bipyridinium derivatives on their photochromism, such as different substituents at nitrogen and coexisting guest species.9 However, that of inorganic anions on photochromic properties in bipyridinium coordination polymers are rarely reported.3c,10 © XXXX American Chemical Society

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EXPERIMENTAL SECTION

Materials and Measurements. All chemical materials were purchased from commercial sources and used without further purification. 1H nuclear magnetic resonance (1HNMR) spectra were recorded on Bruker Avance NMR spectrometer (400 MHz). Fourier Received: January 30, 2016 Revised: March 14, 2016

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DOI: 10.1021/acs.cgd.6b00163 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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transform infrared spectra were taken on a PerkinElmer 2000 spectrometer from KBr pellets in the range 4000−400 cm−1. ESR measurements were performed with a Bruker A300 instrument under ambient atmospheric condition. Powder X-ray diffraction (PXRD) patterns collected on Rigaku Mini Flex-II X-ray diffractometer with Cu Kα (λ = 1.5418 Å) radiation in the range of 5−50° at a rate of 10°/ min. Thermogravimetric analyses (TGA) were carried out on a TG209 system analyzer under nitrogen atmosphere from room temperature to 800 °C at a ramp rate of 10 °C/min. Solid state UV−Vis absorbance studies were carried out with a Varian Cary 500 UV−vis spectrophotometer at room temperature. Synthesis of H2bcbp·2PF6. The organic building block H2bcbp·2Cl was synthesized following the reported process.11 KPF6 (4.60 g, 0.025 mol) was added to H2bcbp·2Cl (4.68 g, 0.01 mol) in 50 mL of distilled H2O, and the mixture was stirred at 80 °C for 2 h. The resulting solid was collected by filtration, washed with water, and dried at 80 °C (Yield: 95%). 1H NMR (400 MHz, DMSO-d6): δ = 13.65 (s, 2H), 9.78 (d, 4H), 9.14 (d, 4H), 8.34 (d, 4H), 8.12 (d, 4H). IR (KBr pellet, cm−1): 3403 (w), 3138 (w), 1729 (s), 1639 (s), 1604 (s), 1492 (m), 1414 (s), 1203 (m), 1104 (s), 829 (m), 737 (s), 637 (m). Synthesis of H2bcbp·2ClO4. KClO4 (0.835 g, 0.006 mol) was added to a solution of H2bcbp·2Cl (0.936 g, 0.002 mol) in 20 mL distilled H2O, then the mixture was stirred at 80 °C for 2 h. Cooling to room temperature, the resulting solid was collected by filtration, washed with water, and dried at 80 °C (yield: 83%). 1H NMR (400 MHz, DMSOd6): δ = 13.63 (s, 2H), 9.77 (d, 4H), 9.13 (d, 4H), 8.34 (d, 4H), 8.13 (d, 4H). IR (KBr pellet, cm−1): 3372 (w), 3128 (w), 1722 (w), 1648 (m), 1611 (s), 1575 (s), 1443 (m), 1405 (s), 1210 (m), 1051 (s), 845 (m), 780 (s), 698 (m). Synthesis of H2bcbp·PO3F. The synthesis procedure of H2bcbp· PO3F is similar to that of H2bcbp·2ClO4, except KClO4 was replaced by Na2PO3F (Yield: 78%). 1H NMR (400 MHz, DMSO-d6): δ = 13.65 (s, 2H), 9.78 (d, 4H), 9.14 (d, 4H), 8.34 (d, 4H), 8.12 (d, 4H). 19F NMR (376 MHz, DMSO-d6): δ = 66.69. IR (KBr pellet, cm−1): 3414 (w), 3098 (w), 1715 (s), 1645 (s), 1614 (s), 1485 (m), 1426 (s), 1197 (m), 1106 (s), 825 (m), 726 (s), 635 (m). Synthesis of Zn2(bcbp)Cl4 (1). A mixture of H2bcbp·2PF6 (14.0 mg, 0.02 mmol) and ZnCl2 (13.6 mg, 0.10 mmol) in a mixed solvent of 0.1 mL of hydrochloric acid (3 M) and 10 mL of methanol was heated at 120 °C for 3 days. Brown crystals of 1 were isolated by filtration, washed with methanol, and dried in air (yield: 36%). IR (KBr pellet, cm−1): 3366 (s), 3059 (w), 2981 (s), 1712 (m), 1606 (s), 1569 (s), 1416 (s), 1046 (s), 840 (m), 776 (m), 703 (m). Synthesis of Zn(bcbp)(PO3F) (2). H2bcbp·2PF6 (14.0 mg, 0.02 mmol) and Zn(NO3)2·6H2O (30.0 mg, 0.10 mmol) were thoroughly dissolved in 3 mL of acetonitrile and 3 mL of methanol. The mixture was heated at 120 °C for 3 days. Yellow crystals of 2 were isolated by filtration, washed with methanol, and dried in air (Yield: 23%). IR (KBr pellet, cm−1): 3356 (m), 3103 (w), 3065 (w), 1638 (m), 1611 (s), 1554 (s), 1379 (s), 1194 (s), 1115 (m), 1051 (m), 840 (m), 776 (s). Synthesis of [CdCl(Hbcbp)(bcbp)]·(ClO4)2 (3). A mixture of H2bcbp·2PF6 (14.0 mg, 0.02 mmol) and Cd(ClO4)2 (21.0 mg, 0.05 mmol) in a mixed solvent of 0.1 mL of hydrochloric acid (3 M), 3 mL of acetonitrile and 3 mL of methanol was heated at 120 °C for 3 days. Yellow crystals of 3 were isolated by filtration, washed with methanol, and dried in air (yield: 28%). IR (KBr pellet, cm−1): 3382 (w), 3116 (w), 1633 (m), 1603 (s), 1568 (m), 1374 (s), 1311 (s), 1014 (m), 835 (m), 787 (s). Synthesis of [Cd2(bcbp)4]·(ClO4)·F3 (4). H2bcbp·2PF6 (14.0 mg, 0.02 mmol) and Cd(ClO4)2 (21.0 mg, 0.05 mmol) were thoroughly dissolved in 3 mL of acetonitrile and 3 mL of methanol. The mixture was heated at 120 °C for 3 days. Brown crystals of 4 were isolated by filtration, washed with methanol, and dried in air (Yield: 42%). IR (KBr pellet, cm−1): 3134 (w), 3070 (w), 1643 (m), 1606 (s), 1551 (s), 1400 (s), 1242 (m), 1078 (s), 830 (s), 776 (s), 623 (m). X-ray Diffraction Analysis. Suitable single crystals of 1−4 were mounted on glass fibers for the X-ray measurement. Diffraction data were collected on a Rigaku-AFC7 equipped with a Rigaku Saturn CCD area-detector system. The measurement was made by using graphite

monochromatic Mo Kα radiation (λ= 0.71073 Å). The frame data were integrated, and absorption correction was calculated using the Rigaku CrystalClear program package. All calculations were performed with SHELXTL-97 program package,13 and structures were solved by direct methods and refined by full-matrix least-squares fitting on F2. All non-hydrogen atoms were refined anisotropically, and hydrogen atoms of the organic ligands were generated theoretically onto the specific atoms. The diffraction data of 2 and 3 were treated by the “SQUEEZE” method as implemented in PLATON to remove diffuse electron density associated with these badly disordered solvent molecules.14 The crystal data and the structure refinements are summarized in Table S1. Crystallographic data have been deposited with the Cambridge Crystallographic Data Center as supplementary publication number CCDC 1448505−1448508 for 1−4. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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RESULTS AND DISCUSSION Synthesis. Solvothermal reaction of H2bcbp·2PF6 and transition-metal salts in mixed solution of acetonitrile and methanol (1:1 in volume) led to a series of coordination polymers. Repeated experiments suggested that a small amount of hydrochloric acid was necessary to obtain compound 1 as pure crystalline phase. During the preparation of compound 2, the PF6− anion was supposed to in situ react with water to form PO3F2− anion, which can be an anionic ligand to coordinate with zinc cation. It is worthy pointing out that such in situ hydrolysis of PF6− may play a key role in the formation of the final crystalline products since no target crystalline materials were obtained by the direct combination of H2bcbp·PO3F with Zn2+. Compounds 3 and 4 were prepared in very similar reaction conditions except that hydrochloric acid was added in the preparation of 3 so that to provide an acidic environment and Cl− during reactions. Crystal Structure of Compound 1. Single crystal X-ray analysis reveals that compound 1 is a 1D coordination polymer. There are one and two halves of Zn2+ cations, two halves of bcbp ligands, and four Cl¯ anions in the asymmetric unit. Each Zn2+ cation is four-coordinated in a distorted tetrahedral geometry by two O atoms (dZn−O = 1.971 (3)−1.984 (3) Å) from two bcbp ligands and two capped Cl¯ anions (dZn−Cl = 2.229 (4)−2.232 (1) Å), as depicted in Figure 1a. In crystal of 1, the deprotonated bcbp ligands exhibit μ4-η1η1-η1-η1 coordination mode to bridge four Zn2+ ions, and each Zn atom is bridged by two bcbp ligands, extending the structure into 1D chain. The capped Cl¯ ions serve as the protruding arms to decorate two sides of the chain. Each chain is aligned in an −ABCDE− stacking mode within the ac plane and held together by π−π interactions (the distance of Cg···Cg is 4.345 Å and the angle is 5.2°) between pyridyl ring and the adjacent phenyl ring to form 2D layer (Figure S9, Supporting Information), which is further arranged in −AB− stacking mode along the b axis (Figure 1c), thus leading to a 3D architecture. Crystal Structure of Compound 2. The asymmetric unit of 2 contains one Zn2+ cation, one bcbp ligand, and one PO3F2− anion. Each of the zinc cations has a slightly distorted tetrahedral coordination environment, with the site occupied by four O atoms from two bcbp ligands and two PO3F2− anions (dZn−O = 1.936 (3)−1.973 (5) Å) (Figure 2a). One prominent structural feature of 2 is the presence of a dinuclear Zn(II) unit (Zn2(CO2)4(PO3F)2). Two Zn(II) ions in the dinuclear unit are doubly bridged by two PO3F2− ions with a Zn···Zn distance of 4.822(2) Å. The dinuclear unit further connects to B

DOI: 10.1021/acs.cgd.6b00163 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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holes of the layers is 26.07 × 43.38 Å, as defined by the largest and shortest distances between the diagonal of rhombus (Figure S11, Supporting Information). The catenated structure feature is obvious, because the resulting 3D coordination polymer network has a higher dimensionality than that of each layer. Closer analysis of the structure reveals a 2D + 2D → 3D inclined polycatenation motif, with an angle of 66.9° between two members of different layer sets (Figure S12, Supporting Information). In Figure 2c, two layers interlock with each other in an incline fashion to give an intercatenated net. While there is no direct covalent interaction between catenated layers, structural stability is provided by hydrogen bonds (C8−H8···O2 = 3.104 Å, ∠C8− H8···O2 = 169.6°), as well as π−π interactions (the distance of Cg···Cg is 3.625 Å and the angle is 16.7°) between pyridyl ring of bcbp and the adjacent phenyl ring. The PO3F2− group in 2 arises from the partial hydrolysis of PF6− anions15 (PF6− + 4H2O → PO3F2− + 5HF + H3O+) as confirmed by the 19F and 31P NMR spectrum (Figures S4−S5, Supporting Information). The 19F and 31P NMR spectrum of 2 shows that a singlet at −72.52 and 3.55 ppm, respectively. These signals are characteristic of PO3F2−. Although the ability of PO3F2− to function as a bridging ligand is known, 2 is the first reported in coordination polymer in which PO3F2− connects zinc(II) centers. Crystal Structure of Compound 3. The asymmetric unit of 3 consists of one independent Cd2+ cation, two bcbp ligands, two ClO4− anions, and one coordinated Cl− anion. As shown in Figure 3a, the Cd2+ cation displays a seven-coordinate environment with distorted pentagonal bipyramidal geometry, which is coordinated by six O atoms (dCd−O = 2.355 (2)−2.538 (2) Å) from three bcbp ligands and one Cl− ion (dCd−Cl = 2.492 (1) Å) (Figure 3a). In the asymmetric unit of 3, among the four carboxyl groups of the two bcbp ligands, only three coordinates to the metal center with a chelating mode, the uncoordinated one forms O−H···O hydrogen bonds (O7−H7A···O3 = 2.615 Å, ∠O7−H7A···O3 = 161.1°) with another coordinated carboxyl group. Each Cd2+ ion is connected by three bcbp ligands to form a 1D T-shaped coordination configuration, with the Cd2+ ion in the horizontal orientations and the uncoordinated carboxyl in the vertical direction. As shown in Figure 3b, the T-shaped units are connected to each other by hydrogen bond interactions resulting in a 2D wavy network (Figure 3c), which is further arranged along the b axis through the π−π interactions (the distance of Cg···Cg is 3.594 Å and the angle is 20.1°) between pyridyl rings of bcbp and the adjacent phenyl rings, thus leading to a 3D supramolecular network. Crystal Structure of Compound 4. Single-crystal X-ray diffraction analysis revealed that compound 4 crystallizes in the monoclinic space group C2/c and is composed of an extrodinarily large, cationic diamondoid framework. The asymmetric unit consists of one Cd2+ ion, two halves of bcbp ligands, and a quarter of ClO4− anion; other disordered anions were not crystallographically well-defined. However, based on the 19F NMR spectrum of 4, the other disordered anion is F− ions (Figure S6, Supporting Information) can be concluded, which may arise from the hydrolysis of PF6− anions.15 Each Cd2+ center is bound to eight carboxylate oxygen atoms (dCd−O = 2.380 (3)−2.481 (5) Å) from four individual bcbp ligands in a distorted antiprismatic manner. The Cd2+ ion can be regarded as a four-connecting tetrahedral node. The bcbp ligand functions as an extended linker, bridging two Cd2+ centers.

Figure 1. Crystal structure of 1: (a) 1D chain; (b) packing diagram for 1 view along the b axis; (c) view along the c axis. All hydrogen atoms are omitted for clarity.

Figure 2. (a) The coordination environment of the Zn atom in 2, symmetry codes: (a) 2 − x, 0.5 − y, z; (b) 1.5 −x, 1 − y, 0.5 + z; (b) the 2D rhombus network in the bc plane; (c) schematic perspective of inclined polycatenation in 2.

neighboring ones through four bcbp ligands, forming a 2D laminar network with rhombus holes in the bc plane (Figure 2b). From a topological viewpoint, these 2D laminar networks containing rhombus holes can be regarded as (4, 4) grid topology if we choose the dinuclear units as nodes and the ligands (bcbp) as connecting rods. The size of the rhombus C

DOI: 10.1021/acs.cgd.6b00163 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 4. (a) Single distorted adamantanoid cage in 4 and its simplification; (b) schematic view of the 13-fold interpenetration along the c-axis; (c) 13 translationally equivalent adamantine cages.

confirm the generation of the radicals, the electron spin resonance (ESR) spectra of 1−4 have been measured before and after irradiation (Figure 6). After irradiation, strong ESR signals at 2.0035, 2.0014, and 2.0028 for compounds 1−3 are observed, which are similar to those found in bipyridinium and viologen complexes.5a,7 This indicates that the bcbp ligand is indeed reduced to generate bcbp•− free radicals after three compounds are irradiated. On the contrary, compound 4 shows no ESR signals before and after irradiation (Figure 6d), which shows again the silence of its photochromism. In order to get further insight into the effect of the anions on the photochromic behaviors for these four compounds, the interactions between anions and bipyridinium moieties of 1−4 were analyzed (Figure 7), which indeed reveals that the distances between anions and centroids of the pyridinium ring are 3.692, 3.308, 3.328, and 3.109 Å, respectively. Such distances are suitable for the occurrence of photoinduced electron transfer reaction between the bipyridinium units and anion electron donors to generate respective radicals.9a,17 Among the factors for designing of photochromic materials, the electron-accepting abilities of the acceptors and the electrondonating abilities of the donors are most important. For crystals 1−4, they possess the same electron acceptor, bcbp moieties. However, because of the different anions, the electron donating abilities of their anions are different in photochromic behaviors. Accordingly, their different photochromic behaviors should mainly be originated from different anion components. It is known that Cl atom is an electron-donating species,3c which can give an electron in redox photochromic metal complexes. Compound 4 does not show any photochromic behavior, which may be attributed to the weak electron-donating ability of ClO4− (probably the energy level does not match between ClO4− and bipyridinium moieties), which leads to the situation that the 4 cannot undergo a photoinduced radical generation upon irradiation. This speculation was substantiated by photochromic studies of H2bcbp·2Cl, H2bcbp·PO3F, and

Figure 3. Coordination environment of the Cd atom in 3, symmetry codes: (a) −2 + x, 0.5 − y, −0.5 + z; (b) hydrogen bonding interactions between two T-shaped chains; (c) 2D wavy network connected by hydrogen bonding interactions. For clarify, all the ClO4− anions are omitted.

As shown in Figure 4a, the presence of a huge distorted adamantanoid cage is apparent. All of the Cd···Cd edge separations equal 23.80(5) Å and the Cd···Cd···Cd angles range from 93.43 to 142.18°, in which an imaginary sphere with a diameter of up to 16 Å could be accommodated (Figure 4a). To minimize the large void cavities in the adamantanoid cages and stabilize the whole structure, a normal 13-fold nonconnected interpenetrating diamondoid framework is formed, related by a single translation corresponding to the crystallographic a-axis, as illustrated in Figure 4c. To our best knowledge, compound 4 shows a very high degree of interpenetration presently known for interpenetrating diamondoid nets.16 Photochromic Properties. Compounds 1−3 are photosensitive, giving a color change from yellow into dark-green or dark upon exposure to UV−vis light in air within 1 min (Figure 5). However, no color changes are observed for compound 4 even irradiated by 10 min. The photoproducts of 1−3 are stable in air but can return to yellow in a dark room for 1 day at room temperature (Figure S16, Supporting Information). In addition, such decolored samples can also display color changes after irradiation again, which indicates reversible photochromism of 1−3. The UV−vis diffuse reflectance spectra of the photochromic products of 1−3 show characteristic bands around 460 and 670 nm. These characteristic spectral bands are similar to that observed for bipyridinium radicals,5a suggesting that the color change of compounds 1−3 may arise from the photoinduced generation of radicals in bcbp molecules. To D

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Figure 5. UV−vis diffuse reflectance spectra and photographs showing the photochromic behavior of 1−4 (a−d); the spectra were recorded when 1−4 were irradiated by UV−vis light (xenon lamp, 300 W) at 1, 1, 1, and 10 min, respectively.

Figure 6. ESR spectra of 1 (a), 2 (b), 3 (c), and 4 (d) in the solid state at room temperature before (black line) and after irradiation (red line). The small ESR signal observed for 2 and 3 should arise from an ambient light-induced photoreaction due to the high photoactivity of 2 and 3.

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ACKNOWLEDGMENTS This work has been supported by National Natural Science Foundation of China (21202020 and 21572032), Doctoral Fund of Ministry of Education of China (20123514120002), Natural Science Foundation of Fujian Province (2014J01040 and 2014J01045).

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Figure 7. Distance between anions ligand and bipyridinium in compounds 1 (a), 2 (b), 3 (c), and 4 (d).

H2bcbp·2ClO4. As shown in Figure S17, H2bcbp·2ClO4 exhibits no photochromic behavior, while H2bcbp·2Cl and H2bcbp·PO3F undergo a color change from light-yellow to gray or dark-brown. Moreover, H2bcbp·2Cl, H2bcbp·PO3F, and H2bcbp·2ClO4 exhibit no ESR signals before irradiation but present single line signals of H2bcbp·2Cl and H2bcbp·PO3F after irradiation (Figure S18, Supporting Information). It is reasonable to think that the photochromism of H2bcbp·2Cl and H2bcbp·PO3F are based on an electron-transfer mechanism. These results indicate that Cl− and PO3F2− anions are more suitable electron-donating anions than ClO4− in these photochromic hybrid materials.

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CONCLUSIONS In summary, four rigid bipyridinium-based coordination polymers have been synthesized. Because of the different electron donating abilities of counteranions, they exhibit different photochromic behaviors upon irradiation. To the best of our knowledge, this is the first example to investigate the influence of the anions on photochromic properties of coordination polymers, which showed that Cl− and PO3F2− anions are more suitable electron-donating ligands than the ClO4− anion for bipyridinium-based photochromic coordination complexes.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.6b00163. Figures for the FTIR spectra; NMR spectra, UV−vis spectral, ESR, TGA, powder XRD, and other photographs (PDF) Accession Codes

CCDC 1448505−1448508 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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REFERENCES

(1) (a) Bouas-Laurent, H.; Dürr, H. Pure Appl. Chem. 2001, 73, 639− 665. (b) Bechinger, C.; Ferrere, S.; Zaban, A.; Spragure, J. Nature 1996, 383, 608−610. (c) Kawata, S.; Kawata, Y. Chem. Rev. 2000, 100, 1777−1788. (d) Andrew, T. L.; Tsai, H. Y.; Menon, R. Science 2009, 324, 917−921. (2) (a) Zahavy, E.; Willner, I. J. Am. Chem. Soc. 1996, 118, 12499− 12514. (b) Yu, C.; Liu, B.; Hu, L. J. Org. Chem. 2001, 66, 919−924. (c) Higashimoto, S.; Azuma, M. Appl. Catal., B 2009, 89, 557−562. (d) Poneti, G.; Mannini, M.; Sorace, L.; Sainctavit, P.; Arrio, M.-A.; Otero, E.; Criginski Cezar, J. C.; Dei, A. Angew. Chem., Int. Ed. 2010, 49, 1954−1957. (e) Wu, J.; Tao, C.; Li, Y.; Yan, Y.; Li, J.; Yu, J. Chem. Sci. 2014, 5, 4237−4241. (f) Li, P.-X.; Wang, M.-S.; Zhang, M.-J.; Lin, C.-S.; Cai, L.-Z.; Guo, S.-P.; Guo, G.-C. Angew. Chem., Int. Ed. 2014, 53, 11529−11531. (g) Sato, O.; Tao, J.; Zhang, Y.-Z. Angew. Chem., Int. Ed. 2007, 46, 2152−2187. (h) Andres, P. R.; Schubert, U. S. Adv. Mater. 2004, 16, 1043−1068. (i) Morimoto, M.; Miyasaka, H.; Yamashita, M.; Irie, M. J. Am. Chem. Soc. 2009, 131, 9823−9835. (3) (a) Wong, H.-L.; Tao, C.-H.; Zhu, N. Y.; Yam, V. W.-W. Inorg. Chem. 2011, 50, 471−481. (b) Sasaki, K.; Nagamura, T. J. Appl. Phys. 1998, 83, 2894−2895. (c) Mallick, A.; Garai, B.; Addicoat, M. A.; Petkov, P. S.; Heine, T.; Banerjee, R. Chem. Sci. 2015, 6, 1420−1425. (d) Cai, L.-Z.; Chen, Q.-S.; Zhang, C.-J.; Li, P.-X.; Wang, M.-S.; Guo, G.-C. J. Am. Chem. Soc. 2015, 137, 10882−10885. (4) (a) Sun, Y.-Q.; Zhang, J.; Ju, Z.-F.; Yang, G.-Y. Cryst. Growth Des. 2005, 5, 1939−1943. (b) Jin, X.-H.; Ren, C.-X.; Sun, J.-K.; Zhou, X.-J.; Cai, L.-X.; Zhang, J. Chem. Commun. 2012, 48, 10422−10424. (c) Li, H.-Y.; Xu, H.; Zang, S.-Q.; Mak, T. C. W. Chem. Commun. 2016, 52, 525−528. (d) Leblanc, N.; Allain, M.; Mercier, N.; Sanguinet, L. Cryst. Growth Des. 2011, 11, 2064−2069. (5) (a) Sun, J.-K.; Zhang, J. Dalton Trans. 2015, 44, 19041−19055. (b) Zhu, Q.-L.; Sheng, T.-L.; Fu, R.-B.; Hu, S.-M.; Chen, L.; Shen, C.J.; Ma, X.; Wu, X.-T. Chem. - Eur. J. 2011, 17, 3358−3362. (c) Luo, F.; Fan, C. B.; Luo, M. B.; Wu, X. L.; Zhu, Y.; Pu, S. Z.; Xu, W.-Y.; Guo, G.-C. Angew. Chem. 2014, 126, 9452−9455. (d) Patel, D. G.; Walton, I. M.; Cox, J. M.; Gleason, C. J.; Butzer, D. R.; Benedict, J. B. Chem. Commun. 2014, 50, 2653−2656. (e) Jiang, Y.-Y.; Ren, S.-K.; Ma, J.-P.; Liu, Q.-K.; Dong, Y.-B. Chem. - Eur. J. 2009, 15, 10742−10746. (f) Fernando, I. R.; Mezei, G. Inorg. Chem. 2012, 51, 3156−3160. (6) (a) Lv, X.-Y.; Wang, M.-S.; Yang, C.; Wang, G.-E; Wang, S.-H.; Lin, R.-G.; Guo, G.-C. Inorg. Chem. 2012, 51, 4015−4019. (b) Sikdar, N.; Jayaramulu, K.; Kiran, V.; Rao, K. V.; Sampath, S.; George, S. J.; Maji, T. K. Chem. - Eur. J. 2015, 21, 11701−11706. (c) Bhosale, S. V.; Jani, C. H.; Langford, S. J. Chem. Soc. Rev. 2008, 37, 331−342. (d) Fu, Z.; Chen, Y.; Zhang, J.; Liao, S. J. Mater. Chem. 2011, 21, 7895−7897. (7) (a) Zhang, C.-J.; Chen, Z.-W.; Lin, R.-G.; Zhang, M.-J.; Li, P.-X.; Wang, M.-S.; Guo, G.-C. Inorg. Chem. 2014, 53, 847−851. (b) Wang, M.-S.; Xu, G.; Zhang, Z.-J.; Guo, G.-C. Chem. Commun. 2010, 46, 361−376. (c) Fu, K.; Ren, C.-X.; Chen, C.; Cai, L.-X.; Tan, B.; Zhang, J. CrystEngComm 2014, 16, 5134−5141. (8) (a) Ma, J.; Deng, H.; Ma, S.; Li, J.; Jia, X.; Li, C. Chem. Commun. 2015, 51, 6621−6624. (b) Sun, X.-L.; Zhu, Q.-Y.; Mu, W.-Q.; Qian, L.W.; Yu, L.; Wu, J.; Bian, G.-Q.; Dai, J. Dalton Trans. 2014, 43, 12582− 12589. (c) Kiriya, D.; Tosun, M.; Zhao, P.; Kang, J. S.; Javey, A. J. Am. Chem. Soc. 2014, 136, 7853−7856. (d) Aulakh, D.; Varghese, J. R.; Wriedt, M. Inorg. Chem. 2015, 54, 1756−1764. (9) (a) Lin, R.-G.; Xu, G.; Wang, M.-S.; Lu, G.; Li, P.-X.; Guo, G.-C. Inorg. Chem. 2013, 52, 1199−1205. (b) Jin, X.-H.; Ren, C.-X.; Sun, J.K.; Zhou, X.-J.; Cai, L.-X.; Zhang, J. Chem. Commun. 2012, 48, 10422− 10424. (c) Tan, B.; Chen, C.; Cai, L.-X.; Zhang, Y.-J.; Huang, X.-Y.; Zhang, J. Inorg. Chem. 2015, 54, 3456−3461.

AUTHOR INFORMATION

Corresponding Authors

*(M.-J.L.) E-mail: [email protected]. *(C.-C.H.) E-mail: [email protected]. Notes

The authors declare no competing financial interest. F

DOI: 10.1021/acs.cgd.6b00163 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

(10) (a) Sun, J.-K.; Wang, P.; Yao, Q.-X.; Chen, Y.-J.; Li, Z.-H.; Zhang, Y.-F.; Wu, L.-M.; Zhang, J. J. Mater. Chem. 2012, 22, 12212− 12219. (b) Ren, C.-X.; Zheng, A.-L.; Cai, L.-X.; Chen, C.; Tan, B.; Zhang, J. CrystEngComm 2014, 16, 1038−1043. (11) Liu, J.-J.; Guan, Y.-F.; Lin, M.-J.; Huang, C.-C.; Dai, W.-X. Cryst. Growth Des. 2015, 15, 5040−5046. (12) (a) Ma, Y.; Cheng, A.-L.; Tang, B.; Gao, E.-Q. Dalton Trans. 2014, 43, 13957−13964. (b) Hoffart, D. J.; Loeb, S. J. Angew. Chem., Int. Ed. 2005, 44, 901−904. (c) Higuchi, M.; Nakamura, K.; Horike, S.; Hijikata, Y.; Yanai, N.; Fukushima, T.; Kim, J.; Kato, K.; Takata, M.; Watanabe, D.; Oshima, S.; Kitagawa, S. Angew. Chem., Int. Ed. 2012, 51, 8369−8372. (d) Sun, J. K.; Cai, L. X.; Chen, Y. J.; Li, Z. H.; Zhang, J. Chem. Commun. 2011, 47, 6870−6872. (13) Sheldrick, G. M. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, 64, 112−122. (14) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13. (15) (a) Fernandez-Galan, R.; Manzano, B. R.; Otero, A.; Lanfranchi, M.; Pellinghelli, M. A. Inorg. Chem. 1994, 33, 2309−2312. (b) Keller, S.; Brunner, F.; Prescimone, A.; Constable, E. C.; Housecroft, C. E. Inorg. Chem. Commun. 2015, 58, 64−66. (c) Dermitzaki, D.; Raptopoulou, C. P.; Psycharis, V.; Escuer, A.; Perlepes, S. P.; Stamatatos, T. C. Dalton Trans. 2014, 43, 14520−14524. (16) (a) He, Y. P.; Tan, Y. X.; Zhang, J. CrystEngComm 2012, 14, 6359−6361. (b) Men, Y. B.; Sun, J.; Huang, Z. T.; Zheng, Q. Y. CrystEngComm 2009, 11, 978−979. (c) Hsu, Y. F.; Lin, C. H.; Chen, J. D.; Wang, J. C. Cryst. Growth Des. 2008, 8, 1094−1096. (d) Tseng, T.W.; Luo, T.-T.; Tsai, C.-C.; Lu, K.-L. CrystEngComm 2015, 17, 2935− 2939. (17) Chen, Z.-W.; Lu, G.; Li, P.-X.; Lin, R.-G.; Cai, L.-Z.; Wang, M.S.; Guo, G.-C. Cryst. Growth Des. 2014, 14, 2527−2531.

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DOI: 10.1021/acs.cgd.6b00163 Cryst. Growth Des. XXXX, XXX, XXX−XXX