基于D(-)/L(+)-对羟基苯甘氨酸配体的两个铜配合物的合成、结构和电化学性质
Syntheses, Crystal Structures and Electrochemical Properties of Two Chiral Cu Complexes Based on D(-)/L(+)-4-Hydroxyphenylglycine
作者单位E-mail
刘曼玉 河北师范大学化学与材料科学学院, 石家庄 050024  
史亚静 河北师范大学化学与材料科学学院, 石家庄 050024  
王兰芝 河北师范大学化学与材料科学学院, 石家庄 050024  
宋会花 河北师范大学化学与材料科学学院, 石家庄 050024 songhuihua@mail.hebtu.edu.cn 
摘要: 利用手性配体D(-)/L(+)-对羟基苯甘氨酸(D/L-Hhpg)与铜盐在溶液法条件下合成2个手性配合物{[Cu(D-hpg)(phen)(NO3)]·1.5H2O}n1)和{[Cu(L-hpg)(phen)(NO3)]·2H2O}n2),(phen=1,10-菲咯啉)。对2个配合物进行了元素分析、红外光谱、粉末X射线衍射、单晶X射线衍射、固态圆二色谱表征及热重-差热分析。配合物12是正交晶系,P212121手性空间群,二者均为1D链状结构并通过氢键作用形成3D超分子结构。有趣的是,配合物12中的配位硝酸根与晶格水分子之间的氢键作用使它们分别生成了沿b轴方向的左手和右手超分子螺旋链。此外,基于配合物12的中心金属离子为Cu(Ⅱ),进一步探究了电化学性能。循环伏安结果表明生成的配合物具有电化学活性,在扫描速率为0.025~1.0 V·s-1范围内,配合物制备的碳糊电极上的电化学过程是由表面控制的。
关键词: D(-)/L(+)-对羟基苯甘氨酸  晶体结构  手性配合物  电化学
基金项目: 国家自然科学基金(No.21776060)、河北省自然科学基金(No.B2018205152)、河北师范大学应用开发基金(No.L2016K03)和河北省引进留学人员资助项目(No.CL201715)资助。
Abstract: Two chiral coordination compounds based on D(-)/L(+)-4-hydroxyphenylglycine (D/L-Hhpg), {[Cu(D-hpg)(phen)(NO3)]·1.5H2O}n (1) and {[Cu(L-hpg)(phen)(NO3)]·2H2O}n (2) (phen=1,10-phenanthroline) have been syn-thesized and characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, solid-state CD spectra and TG-DSC analysis. Compounds 1 and 2 are orthorhombic, P212121 chiral space groups. They are 1D chain structure, which is extended into a 3D supramolecular structure by the hydrogen bond. Interestingly, the compounds 1 and 2 exist left-handed or right-handed supramolecular helix chains along the b axis direction by the hydrogen bond respectively, which is extended by the hydrogen bond between coordinated nitrate anion and lattice water. Furthermore, based on the central metal ions of Cu(Ⅱ), further explored the compounds 1 and 2 of electrochemical properties, Analysis of cyclic voltammetry at varying scan rates (0.03 to 0.13 V·s-1) demonstrates a linear relationship between the anode peak current and the scan rate, indicating a surface-controlled electrochemical process.
Keywords: D(-)/L(+)-4-hydroxyphenylglycine  crystal structure  homochiral coordination compounds  electrochemistry
投稿时间:2018-08-09 修订日期:2019-04-13
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刘曼玉,史亚静,王兰芝,宋会花.基于D(-)/L(+)-对羟基苯甘氨酸配体的两个铜配合物的合成、结构和电化学性质[J].无机化学学报,2019,35(6):1065-1075.
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