Organometallic complexes for non-linear optics .5. Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(C CC(6)H(4)R-4)Cl(dppm)(2)](R=H, NO2, C6H4NO2-4, CH=CHC6H4NO2-4,(E)); X-ray crystal structure of trans-[Ru(C CC6H4C6H4NO2-4,4')Cl(dppm)(2)]

被引：58

作者：

McDonagh, AM

Whittall, IR

Humphrey, MG

Skelton, BW

White, AH

机构：

[1] AUSTRALIAN NATL UNIV,DEPT CHEM,CANBERRA,ACT 0200,AUSTRALIA

[2] UNIV WESTERN AUSTRALIA,DEPT CHEM,NEDLANDS,WA 6907,AUSTRALIA

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1996年 / 519卷 / 1-2期

关键词：

ruthenium; acetylide; alkynyl; non-linear optics; quadratic hyperpolarizabilities; crystal structure;

D O I：

10.1016/S0022-328X(96)06197-9

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of systematically-varied donor-acceptor octahedral ruthenium sigma-acetylide complexes of general formula trans-[Ru(C=CC(6)H(4)R-4)Cl(dppm)(2)] (R=H, NO2, C6H4NO2-4, CH=CHC6H4NO2-4,(E)) has been synthesized. An X-ray structural study of trans-[Ru(C=CC6H4C6H4NO2-4,4')Cl(dppm)(2)] reveals non-planarity of the biphenylene moiety in the solid state. Semi-empirical calculations employing ZINDO were performed on the acetylide complexes and the dichloro species cis- and trans-[RuCl2(dppm)(2)] to evaluate molecular quadratic optical non-linearities, beta; the results are consistent with (a) a significant increase in beta upon incorporation of a strong acceptor substituent, (b) a substantial increase in beta on chain lengthening, and (c) a 50% decrease in non-linearity upon rotation of phenylene-phenylene dihedral angle from coplanarity to orthogonality for the structurally-characterized complex.

引用

页码：229 / 235

页数：7

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