Syntheses, Structures, and Second-Order Nonlinear Optical Properties of Chiral Zinc(II) Coordination Polymers Based on (R)-4-(4-(1-Carboxyethoxy)phenoxy)-3-fluorobenzoic Acid and Effect of the

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• 作者：Han-Tao Ye ; Chang-Yue Ren ; Guang-Feng Hou ; Ying-Hui Yu ; Xin Xu ; Jin-Sheng Gao ; Peng-Fei Yan ; Seik-Weng Ng
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：July 2, 2014
• 年：2014
• 卷：14
• 期：7
• 页码：3309-3318
• 全文大小：680K
• ISSN：1528-7505

文摘

To investigate the construction of novel chiral coordination polymers and the effect of N-donor ligands with different lengths as the second ligand, five new chiral zinc(II) coordination polymers based on (R)-4-(4-(1-carboxyethoxy)phenoxy)-3-fluorobenzoic acid (H₂cpfa), namely, [Zn(cpfa)] (1), [Zn₂(cpfa)₂(biim-4)₂]路2H₂O (2), [Zn₂(cpfa)₂(bix)₂]路2H₂O (3), [Zn₂(cpfa)₂(bix)₂]路CH₃OH路H₂O (4), and [Zn₂(cpfa)₂(bimb)₂]路CH₃OH路H₂O (5) (where biim-4 = 1,1鈥?(1,4-butanediyl)bis(imidazole), bix = 1,4-bis(imidazole-1-ylmethyl) benzene, bimb = 4,4鈥?bis((1H-imidazol-1-yl)methyl)biphenyl), have been synthesized under hydro(solvo)thermal conditions. Their structures are determined by single crystal X-ray diffraction and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), circular dichroism spectra (CD), and thermogravimetric (TG) analyses. Complex 1 features a three-dimensional (3D) rhombic right-handed structure with a rare topology of 5,5T2. Complexes 2鈥?b>5 involving N-donor ligands with different lengths display similar two-dimensional (2D) sq1 networks. Complex 2 is a 2D 4-connected undulated layer with (H₂O)₂ dimers filling in the cavities. Similar 2D undulated layers in complex 3 are connected via O鈥揌路路路O hydrogen-bonds between cpfa^{2鈥?/sup> anions and lattice water molecules to generate a 3D supramolecular structure. In complex 4, 2D (4,4)-sq1 sheets with large cavities form a 2-fold interpenetrated sq1 network, with the two adjacent layers stacking in an ABAB fashion. Complex 5 exhibits a structure very similar to 4, except with double right-handed helical chains available. The structures of above chiral complexes based on H₂cpfa could be affected by the combined N-donor ligands鈥?tuning ability to the coordination number of the Zn(II) center and the coordination configuration of the H₂cpfa ligand. Furthermore, the second-order nonlinear optical properties of complexes 1鈥?b>5 are also studied, and the second-harmonic generation efficiencies of the complexes could be tuned by the introduction of second N-donor ligands.}