三苯基膦和硫醇混合配体亚铜配合物的结构表征

摘要/Abstract

摘要： 本文用膦配体三苯基膦(PPh₃)和巯基配体5-甲氧基苯并咪唑-2-硫醇(L)合成了一例新型亚铜配合物[CuBr(L)(PPh₃)₂]·2CH₃OH (1)。通过X射线单晶衍射、元素分析、热重分析及多种谱学分析对配合物(1)进行了表征。配合物(1)结晶于单斜晶系,空间群为P2₁/c,中心金属离子与溴离子、两个PPh₃的磷原子以及一个L配体的巯基进行配位,得到四配位亚铜单核配合物。此外,配合物(1)在甲醇溶液下的荧光以及固体荧光均为基于PPh₃配体的荷移跃迁(MLCT),不同之处在于PPh₃甲醇溶液中的荧光没有红移,而固体荧光红移了6 nm,显示甲醇溶液状态下的配合物(1)与固体状态下的结构有差异。

关键词: 一价铜配合物, 晶体结构, 谱学性质, 三苯基膦, 5-甲氧基苯并咪唑-2-硫醇

Abstract: In this work, a new Cu(I) complex [CuBr(L)(PPh₃)₂]·2CH₃OH (1) was synthesized using triphenylphosphine (PPh₃) and 5-methoxybenzimidazole-2-thiol (L). The complex was characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetric analysis and other various spectroscopic analyses. X-ray crystallographic analysis reveals that complex (1) crystallizes in the monoclinic system with P2₁/c space group. Each central metal ion is four-coordinated with one bromide ion, two phosphorus atoms from two PPh₃ ligands and one sulphur atom from one L ligand, resulting in a mononuclear complex. In addition, the fluorescence spectra of 1 in methanol solution and solid state show that the emission mechanism belongs to metal-to-ligand charge transfer (MLCT) based on PPh₃. The difference of the fluorescence emission maximum of 1 in the methanol solution is not shifted compared to PPh₃, while red-shifted by 6 nm compared to PPh₃ in solid state, indicating that the structure of 1 in methanol solution is different from that in solid state.

Key words: copper(Ⅰ) complex, crystal structure, spectroscopic property, triphenylphosphine, 5-methoxybenzimidazole-2-thiol

中图分类号:

O641.4

闫丽, 彭绍春. 三苯基膦和硫醇混合配体亚铜配合物的结构表征[J]. 人工晶体学报, 2021, 50(8): 1457-1463.

YAN Li, PENG Shaochun. Structural Characterization of Copper (Ⅰ) Complex Based on Triphenylphosphine and Thioalcohol Mixed Ligands[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(8): 1457-1463.

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