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物理化学学报  2017, Vol. 33 Issue (12): 2480-2490    DOI: 10.3866/PKU.WHXB201706122
论文     
席夫碱Cu(Ⅱ)络合物的超分子螺旋手性及其手性光谱
曹石,曾丽丽,谢菁,万仕刚,李丹,章慧*()
Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy
Shi CAO,Li-Li ZENG,Jing XIE,Shi-Gang WAN,Dan Li,Hui ZHANG*()
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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)](2a2b)、[Cu(dha-R,R/S,S-dpen)](3a3b),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: 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    
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: Schiff base Cu(Ⅱ) complex    Electronic circular dichroism    Vibrational circular dichroism    Single-crystal structure    Supramolecular chiral assembly
收稿日期: 2017-05-05 出版日期: 2017-06-12
中图分类号:  O641  
基金资助: 国家自然科学基金(21273175)
通讯作者: 章慧     E-mail: huizhang@xmu.edu.cn
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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.

Shi CAO,Li-Li ZENG,Jing XIE,Shi-Gang WAN,Dan Li,Hui ZHANG. Supramolecular Helical Chirality of Schiff Base Copper(Ⅱ) Complexes and Their Chiroptical Spectroscopy. Acta Phys. -Chim. Sin., 2017, 33(12): 2480-2490.

链接本文:

http://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201706122        http://www.whxb.pku.edu.cn/CN/Y2017/V33/I12/2480

图1  手性席夫碱Cu(Ⅱ)络合物的分子结构及其缩写
图2  单核手性[M(dha-chxn)]络合物配位内界的三个层次
ComplexColorYeld/%MS(calcd) [M + H]+
[Cu(dha-R-pn)] (1a)purple73436.1 (436.05)
[Cu(dha-S-pn)] (1b)purple70436.1 (436.05)
[Cu(dha-R, R-chxn)] (2a)purple67476.1 (476.08)
[Cu(dha-S, S-chxn)] (2b)purple69476.1 (476.08)
[Cu(dha-R, R-dpen)] (3a)purple79574.2 (574.09)
[Cu(dha-S, S-dpen)] (3b)purple79574.2 (574.09)
表1  手性席夫碱Cu(Ⅱ)络合物的颜色、产率和质谱分析
ItemValue
Crystal form2a2b3a3b
Empirical formulaC22H24CuN2O6C22H24CuN2O6C30H26CuN2O6, C1H4OC30H26CuN2O6
Formula weight475.97475.97606.11574.07
SolventCH3OHCH3OHCH3OHCH3OH
T/K293(2)293(2)203(2)293(2)
Crystal systemOrthorhombicOrthorhombicOrthorhombicOrthorhombic
Space groupP21212P21212P21212P21212
Wavelength/nm0.0710730.0710730.0710730.071073
Unit cell dimensions
a/nm1.08446(10)1.08461(13)1.2198(2)1.22615(6)
b/nm2.4195(3)2.42690(19)1.3929(2)1.39623(8)
c/nm0.75091(8)0.75087(7)1.6318(3)1.63697(8)
β/(°)90909090
Volume/nm31.9703(3)1.9765(3)0.27725(8)2.8025(3)
Z4444
Calculated density/(g·cm-3)1.6051.6001.4520.653
F(000)98898812601188
Final R indices [I > 2σ(I)]R = 0.0581R = 0.0649R = 0.0454R = 0.0874
Flack parameter-0.01(2)-0.01(3)0.019(15)0.03(3)
CCDC No.1059507105950810595091522855
表2  晶体学数据和精修结果
图3  [M(salen)]络合物的四面体扭曲及其绝对构型命名7
图4  手性salen-Ni (Ⅱ)络合物的配位多面体基元及其一维超分子螺旋30
图5  络合物2a和2b的手性超分子螺旋结构(上)和2a的配位基元(下)
complexθ/(°)
[Cu(dha-R, R-chxn)] (2a)18.53
[Cu(dha-S, S-chxn)] (2b)18.47
[Cu(dha-R, R-dpen)] (3a)13.41
[Cu(dha-S, S-dpen)] (3b)13.48
表3  手性[Cu(dha-en)]络合物的θ值
图6  络合物3a和3b的手性超分子螺旋结构(上)和3a的配位基元(下)
图7  手性[Cu(dha)-pn]]络合物的溶液(左)和固体(右)ECD光谱
图8  手性[Cu(dha)-chxn]]络合物的溶液(左)和固体(右)ECD光谱
图9  手性[Cu(dha)-dpen]]络合物的溶液(左)和固体(右)ECD光谱
图10  手性[Cu(dha-chxn)]络合物的溶液VCD光谱
图11  手性[Cu(dha-dpen)]络合物的溶液VCD光谱
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