The platinum salt C[PtL2], where C = [(R)-Ph(Me)HC∗-NMe3]+ and [PtL2]- = radical monoanion based on [4′, 5′: 5, 6][1, 4]dithiino[2,3-b]quinoxaline-1′,3′dithiolato, shows a variety of properties both in solution and in the solid state thanks to the electronic and/or structural features of the ligand. The complex crystallizes in the chiral space group P1 due to the presence of the enantiopure cation (R)-Ph(Me)HC∗-NMe3+, and it shows paramagnetic behavior relatable to the [PtL2]- radical monoanion. This anionic complex is redox active and shows a strong near-infrared absorbance peak at 1085 nm tunable with the oxidation state of the complex. This complex exhibits a proton-dependent emission at 572 nm in solution at room temperature. The excitation band corresponds to the HOMO-1 (π-orbitals of the S2C2S2 system) → LUMO (π-orbitals of the quinoxaline and benzene-like moieties) transition suggesting that emission is mainly ligand centered in character. The luminescent properties are highly unusual, since the emission falls well above the energy of the lowest energy absorption (anti-Kasha behavior). Joint experimental and density functional theory (DFT) and time-dependent DFT studies are discussed to provide a satisfactory structure/property relationship.

A Platinum-Dithiolene Monoanionic Salt Exhibiting Multiproperties, Including Room-Temperature Proton-Dependent Solution Luminescence / Attar, Salahuddin; Espa, Davide; Artizzu, Flavia; Mercuri, M. Laura; Serpe, Angela; Sessini, Elisa; Concas, Giorgio; Congiu, Francesco; Marchio', Luciano; Deplano, Paola. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 55:11(2016), pp. 5118-5126. [10.1021/acs.inorgchem.5b02491]

A Platinum-Dithiolene Monoanionic Salt Exhibiting Multiproperties, Including Room-Temperature Proton-Dependent Solution Luminescence

MARCHIO', Luciano
Membro del Collaboration Group
;
2016

Abstract

The platinum salt C[PtL2], where C = [(R)-Ph(Me)HC∗-NMe3]+ and [PtL2]- = radical monoanion based on [4′, 5′: 5, 6][1, 4]dithiino[2,3-b]quinoxaline-1′,3′dithiolato, shows a variety of properties both in solution and in the solid state thanks to the electronic and/or structural features of the ligand. The complex crystallizes in the chiral space group P1 due to the presence of the enantiopure cation (R)-Ph(Me)HC∗-NMe3+, and it shows paramagnetic behavior relatable to the [PtL2]- radical monoanion. This anionic complex is redox active and shows a strong near-infrared absorbance peak at 1085 nm tunable with the oxidation state of the complex. This complex exhibits a proton-dependent emission at 572 nm in solution at room temperature. The excitation band corresponds to the HOMO-1 (π-orbitals of the S2C2S2 system) → LUMO (π-orbitals of the quinoxaline and benzene-like moieties) transition suggesting that emission is mainly ligand centered in character. The luminescent properties are highly unusual, since the emission falls well above the energy of the lowest energy absorption (anti-Kasha behavior). Joint experimental and density functional theory (DFT) and time-dependent DFT studies are discussed to provide a satisfactory structure/property relationship.
A Platinum-Dithiolene Monoanionic Salt Exhibiting Multiproperties, Including Room-Temperature Proton-Dependent Solution Luminescence / Attar, Salahuddin; Espa, Davide; Artizzu, Flavia; Mercuri, M. Laura; Serpe, Angela; Sessini, Elisa; Concas, Giorgio; Congiu, Francesco; Marchio', Luciano; Deplano, Paola. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 55:11(2016), pp. 5118-5126. [10.1021/acs.inorgchem.5b02491]
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: http://hdl.handle.net/11381/2807727
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 5
  • ???jsp.display-item.citation.isi??? 5
social impact