Structure-Property Relationships in PtII Diimine-Dithiolate Nonlinear Optical Chromophores Based on Arylethylene-1,2-dithiolate and 2-Thioxothiazoline-4,5-dithiolate - Université de Rennes Accéder directement au contenu
Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2012

Structure-Property Relationships in PtII Diimine-Dithiolate Nonlinear Optical Chromophores Based on Arylethylene-1,2-dithiolate and 2-Thioxothiazoline-4,5-dithiolate

Anna Pintus
  • Fonction : Auteur
M. Carla Aragoni
  • Fonction : Auteur
Francesco A. Devillanova
  • Fonction : Auteur
Dominique Lorcy
  • Fonction : Auteur
  • PersonId : 860297
Francesco Isaia
  • Fonction : Auteur
Vito Lippolis
  • Fonction : Auteur
Rebecca A. Randall
  • Fonction : Auteur
Alexandra M. Z. Slawin
  • Fonction : Auteur
J. Derek Woollins
  • Fonction : Auteur
Massimiliano Arca
  • Fonction : Auteur

Résumé

Eighteen new [PtII(N∧N)(S∧S)] complexes [23-40; N∧N = diimine: 2,2′-bipyridine, 1,10-phenanthroline and alkyl/aryl-substituted derivatives; S∧S = arylethylene-1,2-dithiolate (R-edt2-: R = phenyl, 2-naphthyl, 1-pyrenyl), N-substituted 2-thioxothiazoline-4,5-dithiolate (R-dmet2-: R = methyl, ethyl, phenyl)] have been synthesized and characterized by spectroscopic (UV/Vis/NIR, fluorescence) and electrochemical (CV) measurements. Single-crystal X-ray diffraction analysis allowed structural characterization of five of the complexes (27-29, 31, and 37). Structural modifications capable of affecting the nature and energies of the frontier molecular orbitals in these systems were assessed and hybrid DFT and time-dependent (TD) DFT calculations, carried out both in the gas phase and in the presence of several solvents (CH2Cl2, CHCl3, CH3CN, acetone, thf, dmf, dmso, and toluene), allowed the trends observed in the voltammetric data and in the energies of the peculiar solvatochromic visible absorption bands to be rationalized. In addition, to evaluate the second-order nonlinear optical properties of 23-40, first static hyperpolarizability values βtot were calculated both in the gas phase and in CH2Cl2, the highest values being obtained for [Pt(N∧N)(Me-dmet)] complexes (N∧N = 4,4′-diphenyl-2,2′-bipyridine and 4,7-diphenyl-1,10-phenanthroline; βtot = 691 × 10-30 and 604 × 10-30 esu, respectively).

Dates et versions

hal-00843781 , version 1 (12-07-2013)

Identifiants

Citer

Anna Pintus, M. Carla Aragoni, Nathalie Bellec, Francesco A. Devillanova, Dominique Lorcy, et al.. Structure-Property Relationships in PtII Diimine-Dithiolate Nonlinear Optical Chromophores Based on Arylethylene-1,2-dithiolate and 2-Thioxothiazoline-4,5-dithiolate. European Journal of Inorganic Chemistry, 2012, 2012 (22), pp.3577-3594. ⟨10.1002/ejic.201200346⟩. ⟨hal-00843781⟩
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