Uncommon Optical Properties and Silver-Responsive Turn-Off/On Luminescence in a Pt-II Heteroleptic Dithiolene Complex
| Autor: | Salahuddin S. Attar, Luca Pilia, Flavia Artizzu, Paola Deplano, Maria Francesca Casula, Luciano Marchiò, Angela Serpe, Maddalena Pizzotti, Alessio Orbelli‐Biroli, Davide Espa |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
optical properties
crystal structure Quenching (fluorescence) 010405 organic chemistry Chemistry Organic Chemistry Solvatochromism chemistry.chemical_element General Chemistry Crystal structure 010402 general chemistry DFT calculations 01 natural sciences Catalysis 0104 chemical sciences Crystallography Excited state Molecule Hypsochromic shift dithiolenes platinum Luminescence Platinum |
| Zdroj: | Chemistry (Weinh., Print) 24 (2018): 10503–10512. doi:10.1002/chem.201801697 info:cnr-pdr/source/autori:Attar, Salahuddin S.; Artizzu, Flavia; Marchio, Luciano; Espa, Davide; Pilia, Luca; Casula, Maria F.; Serpe, Angela; Pizzotti, Maddalena; Orbelli-Biroli, Alessio; Deplano, Paola/titolo:Uncommon Optical Properties and Silver-Responsive Turn-Off%2FOn Luminescence in a Pt-II Heteroleptic Dithiolene Complex/doi:10.1002%2Fchem.201801697/rivista:Chemistry (Weinh., Print)/anno:2018/pagina_da:10503/pagina_a:10512/intervallo_pagine:10503–10512/volume:24 |
| DOI: | 10.1002/chem.201801697 |
| Popis: | Complex [Pt(iPr(2)pipdt)(Quinoxdt)] (iPr(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 570nm (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(iPr(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. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|