Shi Zhi Qiang, Ji Ning Ning, Hu Hai Liang
College of Chemistry and Chemical Engineering, Taishan University, Taian, Shandong 271021, People's Republic of China.
School of Chemical Engineering, Guizhou Minzu University, Guiyang, Guizhou 550025, People's Republic of China.
Acta Crystallogr C Struct Chem. 2020 Jan 1;76(Pt 1):37-43. doi: 10.1107/S2053229619016024.
By employing the conjugated bithiophene ligand 5,5'-bis(1H-imidazol-1-yl)-2,2'-bithiophene (bibp), which can exhibit trans and cis conformations, two different Cu coordination polymers, namely, poly[μ-5,5'-bis(1H-imidazol-1-yl)-2,2'-bithiophene-κN:N'copper(II)], [Cu(CHO)(CHNS)] or [Cu(bibp)(oba)], (I), and catena-poly[μ-aqua-bis[μ-5,5'-bis(1H-imidazol-1-yl)-2,2'-bithiophene-κN:N']bis(μ-4,4'-oxydibenzoato)-κO:O':O'';κO:O',O'':O'-dicopper(II)], [Cu(CHO)(CHNS)(HO)] or [Cu(bibp)(oba)(HO)], (II), have been prepared through one-pot concomitant crystallization and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, powder X-ray diffraction (PXRD) and thermogravimetric (TG) analysis. Single-crystal X-ray diffraction indicates that the most interesting aspect of the structure is the existence of sole trans and cis conformations of the bibp ligand in a single net of (I) and (II), respectively. Compound (I) displays a threefold interpenetrating three-dimensional framework with a 4-connected {6.8} cds topology, whereas (II) features a one-dimensional chain structure. In the crystal of (II), the polymeric chains are further extended through C-H...O hydrogen bonds and C-H...π interactions into a three-dimensional supramolecular architecture. In addition, strong intramolecular O-H...O hydrogen bonds formed between the bridging water molecules and the carboxylate O atoms improve the stability of the framework of (II). Furthermore, solid-state UV-Vis spectroscopy experiments show that compounds (I) and (II) exhibit optical band gaps which are characteristic for optical semiconductors, with values of 2.70 and 2.26 eV, respectively.
通过使用可呈现反式和顺式构象的共轭联噻吩配体5,5'-双(1H-咪唑-1-基)-2,2'-联噻吩(bibp)，制备了两种不同的铜配位聚合物，即聚[μ-5,5'-双(1H-咪唑-1-基)-2,2'-联噻吩-κN:N'铜(II)]，[Cu(CHO)(CHNS)]或[Cu(bibp)(oba)]，(I)，以及链状聚[μ-水合双[μ-5,5'-双(1H-咪唑-1-基)-2,2'-联噻吩-κN:N']双(μ-4,4'-氧代二苯甲酸根)-κO:O':O'';κO:O',O'':O'-二铜(II)]，[Cu(CHO)(CHNS)(HO)]或[Cu(bibp)(oba)(HO)]，(II)，通过一锅法同时结晶制备，并通过单晶X射线衍射、红外光谱、元素分析、粉末X射线衍射(PXRD)和热重(TG)分析进行表征。单晶X射线衍射表明，结构中最有趣的方面分别是在(I)和(II)的单一网络中bibp配体仅存在反式和顺式构象。化合物(I)呈现具有4连接{6.8} cds拓扑结构的三重互穿三维骨架，而(II)具有一维链结构。在(II)的晶体中，聚合物链通过C-H...O氢键和C-H...π相互作用进一步扩展为三维超分子结构。此外，桥连水分子与羧酸根O原子之间形成的强分子内O-H...O氢键提高了(II)骨架的稳定性。此外，固态紫外-可见光谱实验表明，化合物(I)和(II)表现出光学带隙，这是光学半导体的特征，其值分别为2.70和2.26 eV。
