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ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2017,Vol.33>> Issue(12)>> 2480-2490     doi: 10.3866/PKU.WHXB201706122         中文摘要
Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy
CAO Shi, ZENG Li-Li, XIE Jing, WAN Shi-Gang, Li Dan, ZHANG Hui
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
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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.



Keywords: Schiff base Cu(II) complex   Electronic circular dichroism   Vibrational circular dichroism   Single-crystal structure   Supramolecular chiral assembly  
Received: 2017-05-05 Accepted: 2017-06-02 Publication Date (Web): 2017-06-12
Corresponding Authors: ZHANG Hui Email: huizhang@xmu.edu.cn

Fund: The project was supported by the National Natural Science Foundation of China (21273175)

Cite this article: 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 Phys. -Chim. Sin., 2017,33 (12): 2480-2490.    doi: 10.3866/PKU.WHXB201706122

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