The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N′-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1–3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P–1), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C2S2MS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M–S bond distances involving the two ligands are similar, while the C–S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1–3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1–3 as well as on [Pt(Bz2pipdt)(mnt)] (4) and [Pt(Bz2pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (δ2) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the π system of its dithiolate ligand, dmit.

Role of the acceptor in tuning the properties of metal [M(II) = Ni, Pd, Pt] dithiolato/dithione (donor/acceptor) second-order nonlinear chromophores: Combined experimental and theoretical studies / D., Espa; L., Pilia; C., Makedonas; Marchio', Luciano; M. L., Mercuri; A., Serpe; A., Barsella; A., Fort; C. A., Mitsopoulou; P., Deplano. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 53:2(2014), pp. 1170-1183. [10.1021/ic402738b]

Role of the acceptor in tuning the properties of metal [M(II) = Ni, Pd, Pt] dithiolato/dithione (donor/acceptor) second-order nonlinear chromophores: Combined experimental and theoretical studies

MARCHIO', Luciano;
2014-01-01

Abstract

The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N′-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1–3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P–1), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C2S2MS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M–S bond distances involving the two ligands are similar, while the C–S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1–3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1–3 as well as on [Pt(Bz2pipdt)(mnt)] (4) and [Pt(Bz2pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (δ2) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the π system of its dithiolate ligand, dmit.
2014
Role of the acceptor in tuning the properties of metal [M(II) = Ni, Pd, Pt] dithiolato/dithione (donor/acceptor) second-order nonlinear chromophores: Combined experimental and theoretical studies / D., Espa; L., Pilia; C., Makedonas; Marchio', Luciano; M. L., Mercuri; A., Serpe; A., Barsella; A., Fort; C. A., Mitsopoulou; P., Deplano. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 53:2(2014), pp. 1170-1183. [10.1021/ic402738b]
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2721107
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 31
  • ???jsp.display-item.citation.isi??? 31
social impact