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Uncommon Optical Properties and Silver‐Responsive Turn‐Off/On Luminescence in a Pt II Heteroleptic Dithiolene Complex
Author(s) -
Attar Salahuddin S.,
Artizzu Flavia,
Marchiò Luciano,
Espa Davide,
Pilia Luca,
Casula Maria F.,
Serpe Angela,
Pizzotti Maddalena,
OrbelliBiroli Alessio,
Deplano Paola
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801697
Subject(s) - luminescence , solvatochromism , excited state , polarizability , hypsochromic shift , quenching (fluorescence) , photochemistry , chemistry , platinum , diimine , time dependent density functional theory , quinoxaline , luminophore , crystallography , materials science , density functional theory , fluorescence , computational chemistry , molecule , atomic physics , optics , organic chemistry , physics , optoelectronics , catalysis
Complex [Pt( i Pr 2 pipdt)(Quinoxdt)] ( i Pr 2 pipdt=1,4‐diisopropyl‐piperazine‐2,3‐dithione; Quinoxdt=[1,4]dithiino[2,3‐ b ]quinoxaline‐2,3‐dithiolate) exhibits a remarkable green emission at 570 nm (room temperature), which is above the lowest excited state. The complex is characterized by negative solvatochromism as well as a high second‐order polarizability. Addition of Ag I ions induces 1) hypsochromic shift of the lowest frequencies and 2) reversible quenching of luminescence. The corresponding Ni and Pd complexes have also been prepared and investigated to assist interpretation of optical properties within the triad. Computational studies based on DFT and time‐dependent DFT highlight the electronic properties of [Pt( i Pr 2 pipdt)(Quinoxdt)]. The preferential site of interaction between the Pt complex and incoming Ag I is evidenced by the shape of the Fukui functions, pointing to the thiolic sulfur and platinum atoms as the most reactive sites towards a soft cation. Calculated optical properties are in agreement with experimental findings. This study sheds light on the structure–property relationship for this class of compounds.