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Structure–Property Relationships in Pt II Diimine‐Dithiolate Nonlinear Optical Chromophores Based on Arylethylene‐1,2‐dithiolate and 2‐Thioxothiazoline‐4,5‐dithiolate
Author(s) -
Pintus Anna,
Aragoni M. Carla,
Bellec Nathalie,
Devillanova Francesco A.,
Lorcy Dominique,
Isaia Francesco,
Lippolis Vito,
Randall Rebecca A. M.,
Roisnel Thierry,
Slawin Alexandra M. Z.,
Woollins J. Derek,
Arca Massimiliano
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200346
Subject(s) - chemistry , hyperpolarizability , solvatochromism , diimine , molecular orbital , chromophore , crystallography , alkyl , aryl , photochemistry , molecule , polarizability , organic chemistry , catalysis
Eighteen new [Pt II (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‐edt 2– : R = phenyl, 2‐naphthyl, 1‐pyrenyl), N ‐substituted 2‐thioxothiazoline‐4,5‐dithiolate (R‐dmet 2– : 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 (CH 2 Cl 2 , CHCl 3 , CH 3 CN, 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 β tot were calculated both in the gas phase and in CH 2 Cl 2 , 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; β tot = 691 × 10 –30 and 604 × 10 –30 esu, respectively).