摘要
利用从头算 MP2方法优化了 Pt( CN) 2 ( CNCH3 ) 2 ,Pt( CN) 2 ( CNCH3 ) 2 -( NCCH3 ) 2 .[Pt( CN) 2 ·( CNCH3 ) 2 ]2 的基态几何结构 ;利用单激发的组态相互作用方法 ( CIS)计算了固态和乙氰溶液中标题化合物的发射光谱 ,并对激发态的几何结构进行了优化 .结果表明 :基态时 ,Pt… NCCH3 之间的距离较大( 0 .4 0 6nm) ,说明溶剂分子与 Pt原子之间存在较小的范德华作用 ;而激发态时 ,Pt… NCCH3 之间的距离减小 ( 0 .2 57nm) ,说明此时 Pt… NCCH3 之间相互作用较强 ,由于这种作用使乙氰溶液中该物质的发光性质与不考虑溶剂效应时相比差异较大 .其发射光谱不在可见光谱区 .固态时 ,此化合物为直线链状结构 .MP2计算得到 :基态时 [Pt( CN) 2 ( CNCH3 ) 2 ]2 中 Pt… Pt之间的距离为 0 .3 3 9nm ,电荷布居为 0 .0 3 2 .说明 Pt… Pt间有一定的成键性质 ,这种相互作用促使形成二聚体 ,并影响其固态的发光性质 .
The Optimizations on the ground state structures were performed under the MP2 calculations for Pt(CN) 2(CNCH 3) 2, Pt(CN) 2(CNCH 3) 2 (NCCH 3) 2 and [Pt(CN) 2(CNCH 3) 2] 2. Based on these calculations, single excitation configuration interaction (CIS) calculations were carried out to optimize the molecular structures of the excited states and to reveal the excited state electronic structures. The MP2 calculations showed that the Pt(Ⅱ)…NCCH 3 distance are 0.405 2 nm in ground state 1 A g of Pt(CN) 2(CNCH 3) 2 (NCCH 3) 2, indicating that CH 3CN molecule is weakly interactive with Pt in the ground state. However, the distance became 0.028 10 nm in the excited state, suggestion of a rather strong interaction between Pt(CN) 2(CNCH 3) 2 and the solvent molecule in the NCCH 3 solution. The complex is a linear chain structure at solid state with the Pt(Ⅱ)…Pt(Ⅱ) distance of 0.033 25 nm, which illustrated a typical d 8 d 8 attraction in Pt(Ⅱ) complexes. Therefore, the solvation and the metal metal interaction significantly affect the luminescence of the Pt(CN) 2(CNC 4H 9) 2 complex in the NCCH 3 solution and in solid state respectively. [WT5HZ]
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2000年第12期1908-1912,共5页
Chemical Journal of Chinese Universities
基金
国家自然科学基金!(批准号 :2 9892 168)资助
