两个含有双磷和氮杂环配体的发光铜(Ⅰ)配合物的合成和结构表征

Syntheses and structural characterizations of two luminescent copper(Ⅰ)complexes with diphosphine and N-heterocyclic ligands

从双[(2-二苯膦基)苯基]醚、1,2-双(二苯膦)甲烷配体出发,利用一步法合成了两个新颖的铜(I)配合物[Cu(POP)(C16H6N6)]Br(1)和[Cu2(dppm)2(bphen)2](CF3SO3)2(2)(POP=双[(2-二苯膦基)苯基]醚;C16H6N6=吡唑并[2,3-F][1,10]菲啰啉-2,3-二腈;dppm=1,2-双(二苯膦)甲烷;bphen=4,7-二苯基-1,10-菲啰啉)。并对它们进行了元素分析、红外光谱、X-射线单晶衍射表征和光致发光性质研究。单晶结构分析表明,配合物1是单斜晶系,P2(1)/c空间群,配合物2是单斜晶系,C2/c空间群。在配合物1中Cu(I)与POP和C16H6N6配体螯合,每个Cu(I)分别与POP中的两个磷原子、C16H6N6中的两个氮原子配位形成扭曲的四面体结构。而在配合物2中,dppm通过两个P原子桥连两个Cu(I)形成双核配合物。两个配合物在室温下均发绿光,表现出较强的荧光发射性能,发射光谱峰分别位于537和527 nm。配合物1和2的发射峰均归因于金属到配体的荷移跃迁(MLCT)。

Complexes, [ Cu （POP） （ C,6 H6 N6 ） ] Br （ 1 ） and [ Cu2 （dppm） 2 （bphen） 2 ] （ CF3 SO3 ）2 （ 2 ）, where POP = bis [ 2 - （diphenylphosphino） phenyl ] ether; C 16 H6 N6 = [ 2,3 - f ] - pyrazino - [ 1,10 ] phenanthroline - 2,3 - dicarbonitie ; dppm = bis（diphenylphosphino） methane ; bphen = 4,7 - diphen- yl- 1,10 -phenanthroline, have been newly obtained via an one-step method and characterized by ele- mental analysis, IR spectra, single-crystal X-ray diffraction and photolumineseent measurement. The sin- gle crystal X-ray diffractions reveal that complex 1 is monoelinic in P2（ 1 ）/c space group while complex 2 crystallizes in the monoclinic system with space group C2/c. The Cu（I） is chelated by POP and C16 H6N6 ligands in complex 1. Each Cu（I） is coordinated by two P atoms from POP, two N atoms from C16 HsN6 to form a slightly distorted tetrahedron. While the dppm ligand in complex 2 bridges two Cu（I） through diation two P atoms. In addition, the two complexes emit interesting green luminescence under the irra- of ultraviolet light at room temperature. The emission peaks occur at 537 and 527 nm for complex 1 and complex 2, respectively. The peaks in complex 1 and complex 2 were assigned to the MLCT （ metal to ligand charge transfer）.