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

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. [References: 24]