| 配合物[Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA)的水热合成、晶体结构及量子化学研究 |
| Hydrothermal Synthesis, Crystal Structure and Quantum Chemistry of the Complex [Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA) |
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| 摘要: 以醋酸铜、间三氟甲基苯甲酸(m-TFBA)和邻菲咯啉(phen)为原料在甲醇水介质中通过水热反应，合成了一个新的单核 铜?髤配合物[Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA)，用元素分析、红外光谱和热重分析对配合物进行了表征。X-射线单晶衍射表明，配合物属三斜晶系，空间群P1，晶胞参数：a=1.001 61(10) nm，b=1.150 69(12) nm，c=1.286 49(12) nm，α=82.217(2)°，β=84.767(2)°，γ=66.371(2)°，V=1.344 8(2) nm3，Z=2，Dc=1.625 g·cm-3，R1[I>2σ(I)]=0.042 1，wR2[I>2σ(I)]=0.095 8。铜(Ⅱ)分别与来自邻菲咯啉的2个氮原子、间三氟甲基苯甲酸的1个氧原子和2个水分子中的2个氧原子配位，形成变形的四方锥结构。配合物通过强的O-H…O氢键作用形成了二聚体结构，该二聚体又通过分子间弱的C-H…O氢键作用形成了一维链状结构。配合物中配位的间三氟甲基苯甲酸上的三氟甲基基团具有无序结构。对配合物中[Cu(m-TFBA)(phen)(H2O)2]+进行了量子化学从头计算，探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。 |
| 关键词: 间三氟甲基苯甲酸 邻菲咯啉 铜?髤配合物 晶体结构 从头计算 |
| 基金项目: |
| Abstract: The tiltle complex [Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA) (m-TFBA=m-trifluoromethylbenzoic acid, phen =1,10-phenanthroline) was hydrothermally synthesized by the reaction of cupric acetate monohydrate with m-TFBA and phen in the solvent mixture of methanol and water. The title complex was characterized by elemental analysis, IR spectra and TG. Its crystal structure was determined by X-ray single crystal diffraction study. The crystal belongs to triclinic with space group P1, a=1.001 61(10) nm, b=1.150 69(12) nm, c=1.286 49(12) nm, α=82.217(2)°, β=84.767(2)°, γ=66.371(2)°, V=1.344 8(2) nm3, Z=2, Dc=1.625 g·cm-3, R1[I>2σ(I)]=0.042 1 and wR2[I>2σ(I)]=0.095 8. The copper(Ⅱ) ion is five-coordinated with two nitrogen atoms from one phen, one oxygen atom from one m-TFBA and two water oxygen atoms, forming a distorted square-pyramidal configuration. The -CF3 group from the ligand m-TFBA shows disorder in the title complex. A dimer structure was formed by strong O-H…O hydrogen bonds. Weak intermolecular C-H…O hydrogen bonds link the molecules into one-dimensional chain. The study on the [Cu(m-TFBA)(phen)(H2O)2]+ cation has been performed with quantum chemistry calculation by means of G98W package and taking Lanl2dz basis set. The stabilities of the complex, the orbital energies and composition characteristies of some frontier molecular orbitals have been investigated. CCDC: 735634. |
| Keywords: m-trifluoromethylbenzoic acid 1,10-phenanthroline Copper(Ⅱ) complex crystal structure ab initio method |
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| 季宁宁,石智强,赵仁高.配合物[Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA)的水热合成、晶体结构及量子化学研究[J].无机化学学报,2010,26(6):1025-1030. |
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