Syntheses, crystal structures and photophysical measurements of phosphite-substituted schiff base and azobenzene liâgands

Academic Article

Abstract

  • Organic chromophores with charge asymmetry may exhibit significant second-order nonlinear optical (NLO) properties. Metal complexes have been used as the donor, the acceptor, or as the bridge in some of these chromophores. Metal complexes may also be useful in dipolar chromophore orientation and in the building of large molecular structures, but this approach remains largely unexplored. We herein report the syntheses and characterization of a novel class of phosphite-containing chromophores, O N-1-C H -4-CH=N-1-C H -4-OP(OC H ) (2) and O N-1-C H -4-X=N-1-C H -4-OP(OC H ) [X = CH (3), N (4)], and their transition-metal complexes, cis-Mo(CO) (2) (5), PdCl (2) (6), and cis-Mo(CO) (3) (7). The X-ray crystal structures of 2 and 5 show that coordination of the phosphite ligand to the metal atom does not alter the conformation of the chromophore. Hyper-Rayleigh scattering (HRS) measurements of the compounds in 1,4-dioxane at 1064 nm indicate that phosphite functionalization causes a small decrease in the Î values of the Schiff-base chromophores {Î [esu]: 47âà - â10 (1), 25âà - â10 (2), 30âà - â10 (3} and no change in the Î value of the azo chromophore {Î [esu]: 62âà - â10 (4)}. The larger Î values of the cis-Mo(CO) L complexes {Î [esu]: 38âà - â10 (5), 41âà - â10 (7)} as compared to those of the ligands (2 and 3) are consistent with the 90°orientation of two chromophores in the complexes. A novel class of phosphite-containing chromophores, O N-1-C H -4-CH=N-1-C H -4-OP(OC H ) (2) and O N-1-C H -4-X=N-1-C H -4-OP(OC H ) [X = CH (3), N (4)], and their transition-metal complexes, cis-Mo(CO) (2) (5), PdCl (2) (6), and cis-Mo(CO) (3) (7) were synthesized and fully characterized. Second-order NLO properties of the ligands and complexes were investigated by HRS measurements. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 2 6 4 6 4 6 4 2 2 6 4 6 4 10 6 2 4 2 2 2 4 2 4 2 2 6 4 6 4 6 4 2 2 6 4 6 4 10 6 2 4 2 2 2 4 2 -30 -30 -30 -30 -30 -30
  • Digital Object Identifier (doi)

    Author List

  • Murphy-Jolly MB; Owens SB; Freeman JL; Gray GM; Lawson CM; Shelton DP
  • Start Page

  • 5263
  • End Page

  • 5271
  • Issue

  • 33