Synthesis and Characterization of Transition Metal Systems Containing Phosphino-Oligothiophene Ligands for Nonlinear Optical Materials

Abstract

Polythiophenes exhibit interesting third-order nonlinear optical properties but poor solubilities. Incorporating polythiophenes into transition metal complexes should yield readily soluble materials, and the transition metal substituent may alter third-order nonlinear optical properties of the polythiophene. In this paper, we report the synthesis and characterization of 2-diphenylphosphinothianaphthene, A, and its trans-PdCl 2 L 2 , B, and cis-PtCl 2 L 2 , C, analogues. Additionally 2-diphenylphoshino-5:2′,5′:2′′-terthiophene, D, its trans-PdCl 2 L 2 complex, E, both first prepared by Wolf, 25 the previously unprepared cis-PtCl 2 L 2 analogue, F, and the oxide of A, G, were prepared and investigated for nonlinear optical (NLO) behavior. No appreciable third-order NLO behavior was observed for A, D, or G. However both E and F exhibited nonlinear refraction, as shown by Z-scan measurements, and nonlinear absorption. The nonlinear absorption was significantly stronger for E, indicating that the metal center has a significant affect on nonlinear absorption. This is the first reported observation of this type of nonlinear behavior in metalphosphinothiophene systems.

Syntheses, characterisations and X-ray crystal structures of 5,5′-bis(diphenylphosphino)2,2′-bithiophene derivatives, Ph2(X)P(C4H2S)2P(X)Ph2(X = O, S and CH3+ · I−)

“…Compound 2 was prepared by a modification of a previous procedure [10]. To a solution of 1 (0.65 g, 1.2 mmol) in CHCl 3 (50 mL) and acetone (50 mL) was added 30% H 2 O 2 (0.4 mL), and the mixture was stirred at room temperature overnight.…”

“…E-mail: gmgray@uab.edu incorporated into transition metal complexes that may either be molecular or polymeric depending on the number of phosphorus-donor substituents and the metal center used [6][7][8][9]. Some of the transition metal complexes containing oligothiophene with phosphorus-donor substituents have exhibited very interesting third-order nonlinear optical properties [10].…”

Synthesis and Reactivity of Dinuclear Ni(II) Azido Complexes Containing Bithienylene or Terthienylene Bridging Ligands

“…[1][2][3][4][5][6][7][8][9][10] In particular, group 10 metal dinuclear complexes with linear thiophene arrays are known to be catalytic intermediates in the regioselective reduction of organic thiophenes and are considered as potential materials for electronic or optical molecules.…”

“…In order to investigate the reactivity of the Ni-azido bond in complexes 5-7, they were treated with trimethylsilyl isothiocyanate (TMS-NCS). Complex 5 underwent ligand exchange with two equivalents of TMS-NCS to produce the trans,trans-bis(isothiocyanato) Ni(II) complex (8) in 63% yield as a brown solid (Scheme 3). On the other hand, the same reaction with excess TMS-NCS gave a mixture of 8 (major) and a trace amount of trans-[Ni(NCS) 2 (PEt 3 ) 2 ] (9).…”

1-D networks formed by metal⋯sulfur van der Walls contacts: Novel tetrazole–thiolato Pd(II) and Pt(II) complexes

“…Thiophene compounds with extended p-electron bonds have been intensively studied because of their potential usefulness in the construction of self-assembled compounds and electronic or chemical devices [1][2][3][4][5][6][7][8]. In particular, (a-position)-pyridyl-substituted thiophene derivatives exhibit interesting various coordination behaviors as well as electronic or electroluminescent properties [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23].…”