席夫碱Cu(II)络合物的超分子螺旋手性及其手性光谱

引用本文: 曹石, 曾丽丽, 谢菁, 万仕刚, 李丹, 章慧. 席夫碱Cu(II)络合物的超分子螺旋手性及其手性光谱[J]. 物理化学学报, 2017, 33(12): 2480-2490. doi: 10.3866/PKU.WHXB201706122 shu

Citation: CAO Shi, ZENG Li-Li, XIE Jing, WAN Shi-Gang, Li Dan, ZHANG Hui. Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy[J]. Acta Physico-Chimica Sinica, 2017, 33(12): 2480-2490. doi: 10.3866/PKU.WHXB201706122 shu

席夫碱Cu(II)络合物的超分子螺旋手性及其手性光谱

厦门大学化学化工学院化学系, 福建厦门 361005
基金项目:
国家自然科学基金（21273175）资助项目

摘要: 本文通过不同的手性二胺（pn=1，2-丙二胺、chxn=1，2-环己二胺、dpen=1，2-二苯基乙二胺）与脱氢乙酸（dha）缩合，获得了N₂O₂型手性席夫碱配体（dha-en），进而合成了相应的三对手性席夫碱Cu（Ⅱ）络合物（[Cu（dha-R/S-pn）] （1a和1b）、[Cu（dha-R，R/S，S-chxn）] （2a和2b）、[Cu（dha-R，R/S，S-dpen）] （3a和3b），对其进行的固体和溶液电子圆二色（ECD）及溶液振动圆二色（VCD）光谱测试表明，这些化合物在固体和溶液状态下的金属中心的主要配位模式和绝对构型基本一致。此外，通过单晶结构分析发现：对于络合物2a/2b以及3a/3b，中心金属Cu（Ⅱ）除了与手性dha-en四齿配位外，还与相邻分子内酯环上的羰基发生弱的轴向配位形成一维超分子螺旋链，即实现了配位键构筑的席夫碱络合物的手性超分子自组装。本文对两对手性络合物2a/2b以及3a/3b的手性结构基元及其与超分子螺旋之间的关系进行了讨论。将本文所获实验VCD光谱数据与文献报道的相关数据进行比对分析，可以相互印证，并呈现一定的绝对构型关联规律且具有手性配位立体化学结构的指纹特征。

关键词:

English

Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy

Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
Received Date: 05 May 2017
Revised Date: 02 June 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (21273175)

Abstract: Three pairs of N2O2-type Schiff base ligands were synthesized by condensing dehydroacetic acid (dha) with chiral 1,2-diaminopropane (pn), trans-1,2-diaminocyclohexane (chxn), and 1,2-diphenylethylenediamine (dpen). These chiral ligands were used to coordinate copper(Ⅱ) ions to produce the corresponding Schiff base Cu(Ⅱ) complexes:[Cu(dha-R/S-pn)] (1a and 1b),[Cu(dha-R,R/S,S-chxn)] (2a and 2b), and[Cu(dha-R,R/S,S-dpen)] (3a and 3b). Detailed analyses using electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectroscopies reveal that these Schiff base Cu(Ⅱ) complexes retain the main coordination modes and the absolute configurations of the metal centers, both in solution and the solid state. In addition, according to the crystal structures, the central Cu(Ⅱ) ions of 2a/2b and 3a/3b were found to not only coordinate to the chiral dha-en ligands, but were also axially coordinated to the carbonyl groups of the contiguous lactonic rings, providing one-dimensional supramolecular helical chains through self-assembly. In this work, we deeply studied the relationship between the chiral coordination units and the supramolecular helical structures of 2a/2b and 3a/3b. By comparing our experiment VCD spectroscopic data with related VCD spectral features reported in the literature, a specific correlation between the VCD spectral properties and absolute configurations was investigated, which provided fingerprint characteristics for chiral coordination structure.

Key words:

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席夫碱Cu(II)络合物的超分子螺旋手性及其手性光谱

English

Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy

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席夫碱Cu(II)络合物的超分子螺旋手性及其手性光谱

English

Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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