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    Syntheses and Crystal Structures of Three Ag(I) Complexes with Chloro-phenylacetic Acid and Nitrogen Heterocyclic Ligand①

    2015-03-25 02:35:34HAOXioMinGUChngShengJILiLiHUShiWeiLIYongSONGWenDong
    結(jié)構(gòu)化學(xué) 2015年9期

    HAO Xio-Min GU Chng-Sheng② JI Li-Li HU Shi-Wei LI Yong SONG Wen-Dong②

    a (Department of Applied Chemistry, Guangdong Ocean University,Zhanjiang, Guangdong 524088, China)

    b (Innovation & Application Institute, Zhejiang Ocean University,Zhoushan, Zhejiang 316022, China)

    1 INTRODUCTION

    The rational design and construction of metalorganic frameworks (MOFs) are rapidly expanding in crystal engineering and materials chemistry because of their large numbers of promising applica-tions in many areas, such as luminescence, catalysis,gas storage, ion exchange and so on, as well as for their diverse architectures and topology[1-4]. Controlling the structure and property of MOFs still remains a major challenge in this field because many factors such as organic ligands and central metal ions, temperature, pH value of solution, solvent,hydrogen bonding and π-π stacking interactions also have an efficient effect on assembling the final structure[5-8]. The basic design strategies used for constructing MOFs are based on the nature of interactions between the organic ligand and metal center. Considering the d10closed-cell electronic configuration of silver ions, the preparations of silver complexes have attracted much attention[9].Furthermore, silver ions have a flexible coordination number and irregular coordination spheres which may lead to the discovery of fascinating structures[10].Chloro-benzene carboxylic acids have rich coordination modes such as terminal monodentate,chelating or bridging to more than one metal cation,and therefore they have been extensively employed in the preparation of complexes[11-13]. Heterocyclic nitrogen donors, such as 4,4?-bipyridine and 1,3-bis(4-pyridyl)propane, have also been proved to be among the most important types of organic ligands for the design and construction of coordination polymers exhibiting remarkable properties for their excellent coordinating ability[14-16]. In this study, we introduced chloro-phenylacetic acid with the nitrogen heterocyclic ligands in order to assemble three Ag(I) coordination polymers. In addition, thermal stability, PXRD and fluorescence of the polymers were measured and discussed.

    2 EXPERIMENTAL

    The chemicals were purchased from commercial suppliers and used without further purification.Elemental analyses were performed on a CARLO ERBA 1106 analyzer. It shows the percentage of carbon, hydrogen and nitrogen of the complexes.The FT-IR spectra were recorded on a PerkinElmer Spectrum 100 FT-IR spectrometer using KBr pellet at a resolution of 0.5 cm–1(400~4000 cm–1).Thermogravimetry analyses were performed on an automatic simultaneous thermal analyzer (PE TG/DTA 6300) under a flow of N2at a heating rate of 10 ℃·min–1between ambient temperature and 800 ℃. Luminescence spectra for crystal solid samples were recorded at room temperature on a PERKIN ELMER LS 55 luminance meter. X-ray powdered diffraction pattern of the sample was recorded by an X-ray diffractometer (Rigaku D8)equipped with a graphite-monochromatic CuKα radiation.

    2.1 Synthesis of the complexes

    {[Ag2(2,4-DCPA)(4,4?-bipy)2(NO3)]·(H2O)}n(1):Complex 1 was prepared by the addition of stoichiometric amounts of silver nitrate (0.1699 g, 1 mmol), 2,4-DCPA (0.2050 g, 1 mmol) and 4,4?-bipy(0.3124 g, 2 mmol) dissolved in a 1:1 methanol/water solution (35 mL) and the pH was adjusted to 7 with 0.1 mol/L potassium hydroxide solution.After the mixture was stirred for 30 min, the precipitate was dissolved in the aqueous solution of NH3(25%) which was added drop by drop.Colorless crystals of the compound were obtained by evaporation of the solution for 15 days at room temperature in 52% yield (based on Ag). Analysis calculated for C28H23Cl2N5O6Ag2(%): C, 41.41; H,2.85; N, 8.62. Found (%): C, 41.70; H, 2.90; N, 8.77.IR (KBr pellet, cm-1): 3206(m), 1601(s), 1527(m),1477(m), 1410(w), 1375(s), 1225(m), 1106(m),1068(m), 865(m), 801(m), 726(m), 630(m) and 491(m).

    [Ag(2,4-DCPA)(bpp)]n(2): The synthesis of complex 2 was carried out in the same procedure as that of complex 1, except 4,4?-bipy was replaced by bpp.After reaction, colorless crystals were obtained in 41% yield (based on Ag). Analysis calculated for C21H19Cl2N2O2Ag (%): C, 49.44; H, 3.75; N, 5.49.Found (%): C, 49.60; H, 3.89; N, 5.60. IR(KBr pellet, cm-1): 3353(m), 1562(s), 1501(w), 1419(m),1389(s), 1225(m), 1102(w), 1057(w), 911(w),860(m), 801(m), 715(w), 663(w), 585(m) and 507(m).

    {[Ag(4-DCPA)(bpp)]·(H2O)}n(3): The synthesis of complex 3 was carried out in the same procedure as that of complex 1, except 2,4-DCPA and 4,4?-bipy were substituted by 4-DCPA and bpp,respectively. After reaction, colorless crystals were obtained in 47% yield (based on Ag). Analysis calculated for C21H22ClN2O3Ag (%): C, 51.09; H,4.49; N, 5.67. Found (%): C, 51.34; H, 4.45; N, 5.64.IR (KBr pellet, cm-1): 3416(w), 2947(w), 2361(w),1933(w), 1603(s), 1559(s), 1528(m), 1501(s),1391(m), 1221(m), 1156(m), 1092(m), 1014(m),858(m), 806(s), 677(m), 586(m), 509(s), 450(w).

    2.2 X-ray structure determination

    Colorless single crystals of compounds 1~3(0.26mm × 0.14mm × 0.12mm), (0.30mm ×0.20mm × 0.18mm) and (0.23mm × 0.18mm× 0.16mm) were mounted on glass fibers in a random orientation, respectively. The data were collected on a Bruker SMART APEXII CCD diffractometer at 296(2) K with Mo-Kα radiation (λ =0.71073 ?) by using an ω scan mode in the ranges of 1.71o<θ<25.00o for 1, 2.33o<θ<24.99o for 2 and 1.55o<θ<25.00o for 3. Empirical absorption corrections were carried out by using the SADABS program[17]. The unit cell dimensions were determined by direct methods using the SHELXS program of SHELXTL package and refined with SHELXL[18]. All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were added theoretically, riding on the concerned atoms and refined with fixed thermal factors. For compound 1,the final R = 0.0310 and wR = 0.0832 (w = 1/[σ2(Fo2)+ (0.0444P)2+ 0.6526P], where P = (Fo2+ 2Fc2)/3).S = 1.077, (Δρ)max= 0.698, and (Δρ)min= –0.903 e/?3; for 2, the final R = 0.0315 and wR = 0.0680 (w= 1/[σ2(Fo2) + (0.0324P)2+ 0.7761P], where P =(Fo2+ 2Fc2)/3). S = 1.015, (Δρ)max= 0.522, and(Δρ)min= –0.442 e/?3; for 3, the final R = 0.0296 and wR = 0.0821 (w = 1/[σ2(Fo2) + (0.0560P)2+1.5435P], where P = (Fo2+ 2Fc2)/3). S = 0.974,(Δρ)max= 0.615, and (Δρ)min= –0.745 e/?3. The selected bond lengths, bond angles and H-bonds for 1~3 are given in Tables 1 and 2, respectively.

    Table 1. Selected Bond Lengths (?) and Bond Angles (°)

    Symmetry codes: i x+1, –y+1/2, z+1/2; ii x–1, –y+1/2, z–1/2 for 1. i –x, y+1/2, –z+3/2; ii –x, –y, –z+2; iii –x, y–1/2, –z+3/2 for 2.i x–1/2, –y+1/2, z+1/2; ii –x+1, –y+1, –z+1; iii x+1/2, –y+1/2, z–1/2 for 3

    Table 2. Hydrogen Bond Lengths (?) and Bond Angles (°) for 1 and 2

    3 RESULTS AND DISCUSSION

    3.1 Crystallographic analysis

    3. 1. 1 Crystallographic analysis of complex 1

    The molecular structure of complex 1 is shown in Fig. 1a and the selected bond distances and bond angles are listed in Table 2. Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of 1 contains two Ag(I) cations, three coordinated 2,4-DCPA anions, two coordinated nitrate anions,two 4,4?-bipy ligands and one free water molecule.The silver ions (Ag(1)) are five-coordinated by two different bipy N atoms, two O atoms of nitrates and one carboxylate O atom from 2,4-DCPA ligands, and the local coordination sphere around the Ag(1) ion can be described as a distorted square pyramid with a AgO3N2chromophore. Atoms O(2), O(5), N(3)and N(4)idefine the equatorial plane, while nitrate O(4) atom occupies the apical site (O(2)–Ag(1)–O(5) = 170.58(8)oand N(3)–Ag(1)–N(4)i=166.61(1)o). The Ag(1)–O and Ag(1)–N distances are in the range of 2.167(3)~2.914(1) ?. Moreover,the Ag(2) ions coordinate to two oxygen atoms from the 2,4-DCPA ligands and two nitrogen atoms from different bipy ligands, and the local coordination sphere around the Ag(2) ions can be described as a similar “wedge” shaped with a AgO2N2chromophore (O(1)–Ag(2)–O(2) = 49.51(7)oand N(2)ii–Ag(2)–N(1) = 166.18(10)o). The Ag(2)–N and Ag(2)–O distances fall in the range of 2.154(3)~2.638(2) ?. The 2,4-DCPA ligand is connected to two Ag(I) ions through deprotonated carboxylate groups with η3:μ2coordination modes (chelating/bridging bidentate fashion). The dihedral angle between two pyridine ring planes of bipy ligand is 31.00(1)o(N(1) and N(2) atoms of pyridine ring) and 31.86(1)o(N(3) and N(4) atoms of pyridine ring).One free water molecule (OW) forms an intramolecular hydrogen bond with the coordinated 2,4-DCPA ligand O(1) atom, with the OW–H(1OW)···O(1) bond length of 1.870(2) ? and the bond angle of 169.0(3)o(Table 2).

    Fig. 1. (a) Molecular structure of complex 1 (Symmetry codes: i x+1, –y+1/2, z+1/2; ii x–1, –y+1/2, z–1/2);(b) 2-D structure of complex 1; (c) 3-D structure of complex 1

    All the Ag(I) ions are surrounded by two nitrogen atoms from two bipy ligands form an infinite chain.The adjacent Ag-bipy chains produce “rungs” of a ladder by Ag(1)···Ag(2) interactions (distances 3.2743(5) ?), much shorter than the van der Waals radii of two silver ions (3.440 ?)[19](Fig. 1b). The adjacent Ag···Ag distances of a ladder are 11.378 ?(Ag1···Ag1a) and 11.322 ? (Ag2···Ag2a). The twodimensional layer structure of the compound is formed by intermolecular interactions including intermolecular hydrogen bonds and π···π stackings.There is one kind of intermolecular hydrogen bond types: OW–H(2OW)···O(5)iii= 2.380(2) ? (symmetry code:iiix, –y+1/2, z–1/2). In addition, the 2-D layer structure in complex 1 is further linked through π···π interaction (Cg1···Cg2 = 3.656 ?, the centroids Cg1 are made up of atoms N(1), C(14), C(15), C(16),C(17) and C(18). Moreover, the centroids Cg2 are composed of atoms N(3), C(19), C(20), C(21), C(22)and C(23)). With the help of C–H···π(C(15)–H(15)···Cg = 2.732 ?, the centroids Cg are built by atoms C(3), C(4), C(5), C(6), C(7) and C(8)),adjacent polymeric sheets are assembled to form a supramolecular 3-D network structure (Fig. 1c).

    3. 1. 2 Crystallographic analysis of complex 2

    The X-ray crystal structure of 2 contains silver atom, bpp and 2,4-DCPA anions in the asymmetric unit. Each silver atom is coordinated to two N atoms from two different bpp ligands and two oxygen atoms of one 2,4-DCPA anion. The local coordination sphere around the Ag(1) ion can be described as a similar “wedge” shaped configuration(O(1)–Ag(1)–O(2) = 49.65(8)oand N(2)i–Ag(2)–N(1) = 150.97(9)o). The 2,4-DCPA ligand shows a bidentate chelating mode (Ag(1)–O: 2.570(2) and 2.671(1) ?), and the bpp ligand has adopted two end pyridyl N atoms that link two Ag atoms (Ag(1)–N:2.191(3) and 2.209(2) ?). The interactions (Ag···Ag)also exist in 2 with the Ag(1)···Ag(1)iidistance of 2.999(7) ? (Fig. 2a).

    All the Ag(I) ions are surrounded by two nitrogen atoms from two bpp ligands, forming an infinite chain. The Ag-bpp chains are linked into interesting two-dimensional layers (β-sheet like) by Ag···Ag contact. The Ag1a···Ag1b distance separated by the bpp ligand is 13.0357 ?, and the bpp ligand has a TT conformation (the dihedral angle between two pyridine ring planes of the bpp ligands is 73.563(2)o)(Fig. 2(b))[20]. The 2,4-DCPA ligand is arranged at both sides of the two-dimensional layers with similar“?” model. With the help of C–H···π (C(12)–H(12)···Cg = 3.513 ?, the centroids Cg are made up of atoms C(3), C(4), C(5), C(6), C(7) and C(8)),adjacent polymeric sheets are assembled to form a supramolecular 3-D network structure (Fig. 2 c and d).

    Fig. 2. (a) Molecular structure of complex 2 (Symmetry codes: i –x, y+1/2, –z+3/2; ii –x, –y, –z+2);(b) β-sheet like layers structure of complex 2; (c) 2,4-DCPA ligand in layers on “?” model;(d) 3-D structure of complex 2

    3. 1. 3 Crystallographic analysis of complex 3

    In complex 3, there are silver atoms, one bpp ligand, one 4-DCPA anion and one uncoordinated water molecule in the asymmetric unit. Each silver atom is coordinated by two nitrogen atoms from two bpp ligands and an oxygen atom of the 4-DCPA anions in the T-shaped three-coordinate configuration geometry[21]. The 4-DCPA ligand has adopt a monodentate coordination mode (Ag(1)–O(1) =2.506(3) ?), and the bpp ligand shows two end pyridyl N atoms that connect two Ag atoms(Ag(1)–N: 2.170(3) and 2.182(3) ?). The Ag(1)···Ag(1)iiseparation is 3.0012(7) ?. The uncoordinated water molecule OW forms an intramolecular hydrogen bond with the coordinated 4-DCPA ligands O(2), with the OW···O(2) bond length of 2.844(5) and the OW–H(1W)···O(2) bond angle of 140(7)o(Fig. 3(a) and Table 2).

    Compared to complex 2, a similar β-sheet like layer structure in complex 3 is also found. The Ag1···Ag1a distance separated by bpp ligand is 13.400 ?, and the bpp ligand has a TT conformation(the dihedral angle between two pyridine ring planes of the bpp ligands is 71.839(2)o) (Fig. 3b). The 4-DCPA ligands are arranged at both sides of the layer with similar “S” model. With the help of hydrogen-bonded interactions between adjacent 2D sheets (OW–H(1W)···O(2) and OW–H(2W)···O(1)iv= 2.904(5) ?, symmetry codes:iv–x+1/2, y+1/2,–z+1/2), a supramolecular 3-D network structure(Fig. 3(c) and (d)) is found.

    Fig. 3. (a) Molecular structure of complex 3 (Symmetry codes: i x–1/2, –y+1/2, z+1/2; ii –x+1, –y+1, –z+1);(b) β-sheet like layer structure of complex 3; (c) 4-DCPA ligand in layers on “S” model;(d) 3-D structure of complex 3

    3.2 IR spectrum

    The asymmetric vas(COO–) and symmetrical vs(COO–) appear in 1601, 1477 and 1375 cm–1of complex 1. The two values of Δ(COO–) suggest the presence of two different coordinated modes of the carboxylate groups[22]. In complexes 2 and 3, the strong bands at 1562 and 1603 cm–1are assigned to the asymmetrical vas(COO–), while the shoulders at 1389 and 1391 cm-1correspond to the symmetrical vs(COO–), respectively. The separations (Δv)between vas(COO–) and vs(COO–) are 173 and 212 cm–1, indicating bidentate and monodentate coordinating modes in 2 and 3, respectively. Meanwhile,the bands at 1527, 1501 and 1528 cm–1are assigned to the stretching vibration of -N=C- of pyridyl in 1, 2 and 3, respectively. In addition, the absorptions at 1225, 1068, 801 and 726 cm–1in 1 belong to the absorption band of NO3–groups[23].

    3.3 Thermal analysis

    Fig. 4. Thermogravimetric curves (TG) for complex

    In complexes 1 and 3, the first corresponding to the escape of one free water molecule is observed from 30 to 131 and 128 ℃ (Obsd. 2.63 and 2.94%,Calcd. 2.22 and 2.65%, respectively). The second corresponding to the departure of nitrate anion,2,4-DCPA and 4,4?-bipy ligand is observed from 132 to 668 ℃ (Obsd. 72.46%, Calcd. 71.34%) in complex 1. In complexes 2 and 3, the weight loss step occurred from 142 to 558 ℃ and 128 to 305 ℃ (Obsd. 77.74 and 64.29%, Calcd. 78.83 and 63.28%) due to the decomposition of the framework structure of chloro-aromatic carboxylic acids and bpp ligands, respectively. The final decomposition products by further heating complexes 1, 2 and 3 are all characterized to be metallic silver, with a total weight loss of 25.11, 22.26 and 20.52% (Calcd.26.44%, 21.17 and 21.87%), respectively (Fig. 4)[24].

    3.4 X-ray powder diffraction

    As shown in Fig. 5, the peak positions of the experimental patterns are in agreement with the simulated ones from single-crystal X-ray diffraction,which clearly demonstrates good purity of 1 and 2.There are a few unindexed diffraction differences between the measured and simulated patterns, which may be related to the different orientations of the crystals in the powdered samples.

    Fig. 5. PXRD patter for complexes 1 and 2 (black: simulation of single crystal; red: solid samples)

    3.5 Photoluminescent properties

    In this study, fluorescent property of compound 3 has been investigated in the solid state. Two emission peaks at about 356 nm (λex= 297 nm)[25]and 455 nm (λex= 372 nm)[26]were observed for free 4-DCPA and bpp ligands, respectively. On complexation of these ligands with Ag(I) atoms,strong fluorescence with emission peak at about 485 nm (λex= 286 nm) for the compound is observed at room temperature (Fig. 6), while the emissions arising from the free ligands are not observed. The absence of ligand-based emission suggests energy transfer from the ligands to the Ag(I) atoms during photoluminescence. Therefore, the photoluminescence can probably be assigned to the ligand-toligand charge-transfer transitions[27]. Fluorescence has hardly been ever observed in complexes 1 and 2,which may be attributed to heavy atom effects[28].

    Fig. 6. Solid-state photoluminescent spectrum for complex 3

    4 CONCLUSION

    The complexes of {[Ag2(2,4-DCPA)(4,4?-bipy)2(NO3)]·(H2O)}n(1), [Ag(2,4-DCPA)(bpp)]n(2)and {[Ag(4-DCPA)(bpp)]·(H2O)}n(3) were synthesized and characterized. In complex 1, the Agbipy chains are linked into “rungs” of a ladder by silver(I) ion contacts. In complexes 2 and 3, the two-dimensional β-sheet like layers are observed by Ag···Ag interactions. Complex 3 emits the intense luminescence with the fluorescence of 485 nm in the solid state at room temperature.

    (1) Yun, R. R.; Lu, Z. Y.; Pan, Y.; You, X. Z.; Bai, J. F. Formation of a metal-organic framework with high surface area and gas uptake by breaking edges off truncated cuboctahedral cages. Angew. Chem. Int. Ed. 2013, 52, 11282-11285.

    (2) Cui, Y. J.; Yue, Y. F.; Qian, G. D.; Chen, B. L. Luminescent functional metal-organic frameworks. Chem. Rev. 2012, 112, 1126-1162.

    (3) Wang, J.; Zhao, X. Q. Recent advances of lanthanide-transition heterometallic coordination polymers. Chin. J. Struct. Chem. 2014, 33, 7-18.

    (4) Hao, X. M.; Gu, C. S.; Han, S. Y.; Miao, Y. L.; Li, Y.; Song, W. D. Syntheses and crystal structures of Cd(II) and Ni(II) complexes containing flexible sulfide and nitrogen heterocyclic ligands. Chin. J. Struct. Chem. 2015, 34, 408-416.

    (5) Yeh, C. W.; Chen, T. R.; Chen, J. D.; Wang, J. C. Roles of anion and solvent in the self-assembly of silver(I) complexes containing 2,3-diphenylquinoxaline. Cryst. Growth Des. 2009, 9, 2595-2603.

    (6) Hao, X. M.; Chen, G.; Gu, C. S.; Liu, J. W. The two-dimensional coordination polymer poly[diaqua(μ2-1H-imidazo[4,5-f][1,10]phenanthroline)-μ4-sulfato-μ3-sulfato-dicadmium(II)]. Acta Cryst. C 2014, 70, 770–772.

    (7) Lin, Z. J.; Lv, J.; Hong, M. C.; Cao, R. Metal-organic frameworks based on flexible ligands (FL-MOFs): structures and applications. Chem. Soc. Rev.2014, 43, 5867-5895.

    (8) Su, Z.; Fan, J.; Okamura, T. A.; Sun, W. Y.; Ueyama, N. Ligand-directed and pH-controlled assembly of chiral 3d-3d heterometallic metal-organic frameworks. Cryst. Growth Des. 2010, 10, 3515-3521.

    (9) Hao, X. M.; Chen, G.; Gu, C. S.; Liu, J. W. Poly[μ7-sulfanediyldiacetato-disilver(I)]. Acta Cryst. C 2013, 69, 826–828.

    (10) Xie, J.; Huang, Y. Q.; Okamura, T. A.; Sun, W. Y.; Ueyama, N. Anion effect on structure of silver(I) complexes with new unsymmetrical tripodal ligand. Z. Anorg. Allg. Chem. 2007, 633, 1211-1216.

    (11) Hao, X. M.; Chen, G.; Gu, C. S. A new two-dimensional silver coordination polymer constructed by 1,3-bis(4-pyridyl)propane and 2,6-dichlorophenylacetic acid: synthesis, structure, luminescence and thermal stable properties. Asian. J. Chem. 2014, 26, 5805-5808.

    (12) Gu, C. S.; Hao, X. M.; Guan, S. X.; Liu, J. W. Poly[[μ-aqua-bis(μ-2,4-dichlorophenoxyacetato)barium(II)] monohydrate]. Acta Cryst. C 2006, 62,516-518.

    (13) Shi, S. M.; Chen, Z. F.; Liu, Y. C.; Mao, L.; Liang, H.; Zhou, Z. Y. Synthesis and crystal structures of lanthanide complexes with foliage growth regulator: phenoxyalkanoic acid. J. Coord. Chem. 2008, 61, 2725-2734.

    (14) Li, G. L.; Liu, G. Z.; Huang, L. L.; Li, Z. X. A Novel 3D Cu(II) coordination polymer containing mixed ligands: synthesis, crystal structure and properties. Chin. J. Struct. Chem. 2014, 33, 942-946.

    (15) Hao, X. M.; Chen, G.; Gu, C. S. Synthesis, structure, luminescence and thermal stable properties of Zn(II) coordination polymer constructed from 2-hydroxyphenylacetic acid and 4,4?-trimethylenendipyridine. Asian J. Chem. 2014, 26, 5735-5738.

    (16) Hao, X. M.; Chen, G.; Gu, C. S.; Liu, J. W. A three-dimensional cadmium(II) coordination polymer:poly[[[μ-4,4?-(propane-1,3-diyl)dipyridine-κ2N:N](μ-3,3?-thiodipropionato-κ3O,O?:O)cadmium(II)]monohydrate]. Acta Cryst. C 2014, 70, 712–714.

    (17) Sheldrick, G. M. SADABS, Siemens Area Detector Absorption Corrected Software. University of G?ttingen, Germany 1996.

    (18) Sheldrick, G. M. SHELXL-97, Program for the Refinement of Crystal Structure. University of G?ttingen, Germany 1997.

    (19) Jung, O. S.; Kim, Y. J.; Lee, Y. A.; Park, J. K.; Chae, H. K. Smart molecular helical springs as tunable receptors. J. Am. Chem. Soc. 2000, 122,9921-9925.

    (20) Marinho, M. V.; Yoshida, M. I.; Guedes, K. J.; Krambrock, K.; Bortoluzzi, A. J.; Ho1rner, M.; Machado, F. C.; Teles, W. M. Synthesis, crystal structure, and spectroscopic characterization of trans-bis[(μ-1,3-bis(4-pyridyl)propane)(μ-(3-thiopheneacetate-O))-(3-thiopheneacetate-O)]dicopper(II), {[Cu2(O2CCH2C4H3S)4μ-(BPP)2]}n: from a dinuclear paddle-wheel copper(II) unit to a 2-D coordination polymer involving monatomic carboxylate bridges. Inorg. Chem. 2004, 43, 1539-1544.

    (21) Tong, M. L.; Wu, Y. M.; Ru, J.; Chen, X. M.; Chang, H. C.; Kitagawa, S. Pseudo-polyrotaxane and β-sheet layer-based three-dimensional coordination polymers constructed with silver salts and flexible pyridyl-type ligands. Inorg. Chem. 2002, 41, 4846-4848.

    (22) Gao, S.; Liu, J. W.; Huo, L. H.; Xu, Y. M.; Zhao, H. A two-dimensional Cd(II) coordination polymer: [Cd(1,4-BDOA)(1,10-phen)]·H2O with strong blue fluorescent emission constructed by benzene-1,4-dioxydiacetate ligand. Inorg.Chem.Commun. 2005, 8, 361-364.

    (23) Weng, S. F. Fuliye Bianhuan Hongwai Guangpu Fenxi: Vol.2. Beijing, Chemical industry Press 2010.

    (24) Mürsel, A.; Okan, Z. Y.; Seda, K.; Murat, T. A three-dimensional silver(I) framework assembled from 3,3?-thiodipropionate: synthesis, structure and molecular simulations for hydrogen gas adsorption. Polyhedron 2012, 45, 103-106.

    (25) Xue, J. L.; Tian, C. H. Lead(II) coordination with 4-chlorophenylacetic acid as ligand: structure, luminescence and biological bctivity. Chin. J. Inorg.Chem. 2014, 30, 907-912.

    (26) Liu, Q. Y.; Xu, L. (H2O)12-containing infinite chain encapsulated in supramolecular open framework built of cadmium(II), 1,3-di(4-pyridyl)propane and 5-sulfoisophthalic acid monosodium salt. CrystEngComm. 2005, 7, 87-89.

    (27) Hao, X. M.; Gu, C. S.; Han, S. Y.; Fan, Y. Z.; Li, Y.; Song, W. D. Synthesis, crystal structures of Zn(II) and Mn(II) complexes with flexible sulfur containing aromatic acid and nitrogen heterocyclic ligands. Chin. J. Inorg. Chem. 2015, 31, 369-376.

    (28) Kasha, M. Collisional perturbation of spin-orbital coupling and the mechanism of fuorescence quenching. A visual demonstration of the perturbation.J. Chem. Phys. 1952, 20, 71-74.

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