H…Cl(O),π…π作用的三维配合物[Cu(phen)_2 Cl(ClO_4)]_n的结构和量子化学研究(英文)  

Structure and quantum chemistry of the H…C1(O) and π…π interaction of three-dimensional complex [ Cu (phen) _2 Cl (C1O_4) ]_n

作　　者：邝代治[1] 冯泳兰[1] 王剑秋[1] 张复兴[1] 许志锋[1] 

机构地区：[1]衡阳师范学院化学与材料科学系,湖南衡阳421008

出　　处：《计算机与应用化学》2006年第12期1188-1192,共5页Computers and Applied Chemistry

基　　金：湖南省自然科学基金(05JJ40015,00JJY2010);基础研究(03JZY3036)项目资助~~

摘　　要：通过Cu(ClO4)2和phen(phen=1,10-邻啡罗啉)合成配合物[Cu(phen)2Cl(ClO4)]n,并表征其结构,晶体结构为单斜晶系,空间群为P21／c,晶体学参数:a=1．2666(2)nm,b=1．1219(2)nm,c=1．7225(2)nm,β=111．462(8)°,V=2．2779 (6)nm3,wR=0．071。在晶体中两个邻啡罗啉氮与中心铜离子配位形成2个五元环,4个氮和氯原子与中心铜形成变形四面锥,配合物之间邻近邻啡罗啉的芳环通过π…π作用形成一维结构,通过Cl…H和O…H“氢键”作用形成三维结构,邻近邻啡罗啉的芳环相互平衡组成π…π作用形成一维结构。量子化学(HF／LanL2DZ)计算表明,在配合物中HOMO电子(由铜原子的d轨道、氯和氮的p轨道)向LUMO和LUMO-1(碳原子的p轨道)转移。The complex [ Cu （phen） 2 Cl （ CIO4 ） ]. （ phen = 1,10-phenanthroline） has been synthesized and structurally characterized. It crystallizes in the monoclinic system, space group P21/c with a = 1. 2666（2） nm, b = 1. 1219（2） nm, c = 1. 7225（2） nm, β = 111. 462 （ 8 ）°, V = 2.2779 （6） nm^3, wR = 0.071. In the complex, the Cu （Ⅱ） center is coordinated by the N-atoms of two phenanthroline forming two five-membered chelate rings. The copper ion has a slightly distorted square pyramidal configuration with four nitrogen atoms from phen, and one chloride anion. There are hydrogen bonds, in which the coordinated CA^- （Cl..-H） and dissociate ClO4^- anions （ O... H） link the [ Cu （phen） 2 CA （ ClO4 ） ], respectively. The hydrogen bonds interactions link the complex into a three-dimensional complex [ Cu（phen） 2 CA（ ClO4 ）]. structure. The neighboring aromatic rings of phen moiety between the adjacent complex are parallel to each other and separated by approximately 0. 3388 nm, indicating the presence of significant face-to-face π…π stacking interac- tions. The π…π interactions link the complex into a quasi-one-dimensional structure. The structural calculation were performed on the HF and LanL2DZ levels, and shows the electron are transferred from HOMO to LUMO and LUMO-1 in the complex, that is from d orbital of copper atom with p orbital of chlorine and nitrogen atom to p orbital of carbon.

关 键 词：铜配合物 晶体结构 氢键 量子化学 

分 类 号：O641[理学—物理化学]