In this contribution, we report the design and theoretical analysis, using the INDO/SCI-SOS quantum chemical formalism, of novel molecular architectures based on planar [N-4]-, (2-aminobenzylideneiminato)- and tetraazamacrocycle-coordinated nickel(II) complexes, having second-order nonlinear optical (NLO) properties. Calculations indicate that these molecules possess comparable, or even larger, second-order nonlinearity to the bis(salicylaldiminato)Ni-II Schiff-base analogues. The nonlinearity of substituted complexes is dominated by the nature and position of substituents on the tribenzo[b,f,l] and/or cyclotetradecine rings, and is determined by the relative directions of the ground- and excited-state dipole moments. Moreover, substitution with acceptor groups in the dibenzo[b,l] rings involves a significant octupolar contribution to optical nonlinearity. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Second-order nonlinear optical properties of tetraaza-coordinated nickel(II) complexes
DI BELLA, Santo;
2003-01-01
Abstract
In this contribution, we report the design and theoretical analysis, using the INDO/SCI-SOS quantum chemical formalism, of novel molecular architectures based on planar [N-4]-, (2-aminobenzylideneiminato)- and tetraazamacrocycle-coordinated nickel(II) complexes, having second-order nonlinear optical (NLO) properties. Calculations indicate that these molecules possess comparable, or even larger, second-order nonlinearity to the bis(salicylaldiminato)Ni-II Schiff-base analogues. The nonlinearity of substituted complexes is dominated by the nature and position of substituents on the tribenzo[b,f,l] and/or cyclotetradecine rings, and is determined by the relative directions of the ground- and excited-state dipole moments. Moreover, substitution with acceptor groups in the dibenzo[b,l] rings involves a significant octupolar contribution to optical nonlinearity. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
