Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 22, Pages 3577-3594Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201200346
Keywords
Solvatochromism; Platinum; Nonlinear optics; Density functional calculations; N ligands; S ligands
Categories
Funding
- Universita degli Studi di Cagliari
- Regione Autonoma della Sardegna
- Consorzio interuniversitario per le Applicazioni di Supercalcolo Per Universita e Ricerca (CASPUR)
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Eighteen new [PtII(N?N)(S?S)] complexes [2340; 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 (2729, 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 2340, first static hyperpolarizability values beta tot 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; beta tot = 691 x 1030 and 604 x 1030 esu, respectively).
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