H…Cl(O),π…π作用的三维配合物[Cu(phen)2Cl(ClO4)]n的结构和量子化学研究

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。

Structure and quantum chemistry of the H…Cl(O) and π…π interaction of three-dimensional complex [Cu(phen)2Cl(ClO4)]n

The complex Cu(phen)2Cl(ClO4)]n ( 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) nm3, 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 Cl- (Cl…H) and dissociate ClO4- anions (O…H) link the Cu(phen)2Cl(ClO4)], respectively. The hydrogen bonds interactions link the complex into a three-dimensional complex Cu(phen)2Cl(ClO4)] n 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 interactions. 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.