物理化学学报2017，Vol.33Issue(12)：2480-2490,11.DOI:10.3866/PKU.WHXB201706122
席夫碱Cu(Ⅱ)络合物的超分子螺旋手性及其手性光谱
Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ)Complexes and Their Chiroptical Spectroscopy
摘要
Abstract
Three pairsof 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)] (1aand1b), [Cu(dha-R,R/S,S-chxn)] (2aand2b), and [Cu(dha-R,R/S,S-dpen)] (3aand3b). 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 of2a/2band3a/3bwere 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 coordinationunits and the supramolecular helical structures of2a/2band 3a/3b.By comparing our experiment VCD spectroscopicdatawith related VCD spectral features reported in the literature,aspecificcorrelation between the VCD spectral properties and absolute configurations wasinvestigated, whichprovidedfingerprint characteristics for chiral coordination structure.关键词
席夫碱Cu(Ⅱ)络合物/电子圆二色/振动圆二色/单晶结构/超分子手性组装Key words
Schiff base Cu(II) complex/Electronic circular dichroism/Vibrational circular dichroism/Single-crystal structure/Supramolecular chiral assembly分类
化学化工引用本文复制引用
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):2480-2490,11.基金项目
The project was supported by the NationalNatural Science Foundation of China(21273175).国家自然科学基金(21273175)资助项目 （21273175）
