Organometallic complexes for non-linear optics V Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(C?CC6H4R-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

Abstract

Abstract A series of systematically-varied donor-acceptor octahedral ruthenium σ-acetylide complexes of general formula trans -[Ru(CCC 6 H 4 R-4)Cl(dppm) 2 ] (R = H, NO 2 , C 6 H 4 NO 2 -4 CHCHC 6 H 4 NO 2 -4,( E )) has been synthesized. An X-ray structural study of trans - [Ru(CCC 6 H 4 C 6 H 4 NO 2 -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 -[RuCl 2 (dppm) 2 ] to evaluate molecular quadratic optical non-linearities, β; the results are consistent with (a) a significant increase in β upon incorporation of a strong acceptor substituent, (b) a substantial increase in β 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.