Square-planar d8 metal mixed-ligand dithiolene complexes as second order nonlinear optical chromophores: Structure/property relationship

The structure/property relationship of square-planar d(8) metal push/pull mixed-ligand dithiolene complexes is discussed to provide suitable tools to chemists for tailoring compounds with predictable optical properties. These complexes exhibit a typical HOMO-LUMO electronic transition which falls at low energies (vis-NIR region). Substituents at the dithiolene core affect the energy of the frontier orbitals and mixed-ligand complexes based on two different ligands give rise to an asymmetric-symmetric distribution of the charge according to the differences in the push/pull character of the two ligands. Where the push/pull character of the two ligands is significantly different, a pi localized electron distribution occurs. The pull ligand (dithiolate) contributes mostly to the HOMO, the push ligand (dithione) mostly to the LUMO, and the HOMO-LUMO transition has ligand-to-ligand charge-transfer (CT) character with some contribution of the metal. These chromophores exhibit negative solvatochromism and molecular first hyperpolarizability. Where the difference in the push/pull character of the two ligands is small, a pi-delocalized electron distribution occurs and the chromophores exhibit optical features typical of symmetrical complexes (NIR dyes, no second order NLO activity). Structural data, spectroscopic and electrochemical features reflect the pi-delocalized/localized electron distribution, and suitable markers such as lambda(max), epsilon; nu(C=C); reduction potentials work well to distinguish the limiting forms and to predict optical properties. Analogies in the optical features exhibited by d(8) metal diimino-dithiolate complexes are highlighted. (C) 2009 Elsevier B.V. All rights reserved.