Uncommon Optical Properties and Silver‐Responsive Turn‐Off/On Luminescence in a PtII Heteroleptic Dithiolene Complex. Issue 41 (21st June 2018)

• Record Type: Journal Article
• Authors: Attar, Salahuddin S.; Artizzu, Flavia; Marchiò, Luciano; Espa, Davide; Pilia, Luca; Casula, Maria F.; Serpe, Angela; Pizzotti, Maddalena; Orbelli‐Biroli, Alessio; Deplano, Paola
• Is Part Of: Chemistry. Volume 24:Issue 41(2018)
• Page Start: 10503
• Page End: 10512
• Publication Date: 2018-06-21
• Subjects: crystal structure -- DFT calculations -- dithiolenes -- optical properties -- platinum; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201801697
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Complex [Pt( i Pr2 pipdt)(Quinoxdt)] ( i Pr2 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 Pr2 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. Abstract : One of a kind ! The optical properties of the depicted compound (see figure), apparent anti‐Kasha emission, switchable for silver addition/removal, and 2nd NLO activity, were elucidated herein by combined experimental and theoretical studies.