期刊
DYES AND PIGMENTS
卷 194, 期 -, 页码 -出版社
ELSEVIER SCI LTD
DOI: 10.1016/j.dyepig.2021.109622
关键词
Platinum (II) complexes; Pyrimidine; NNC ligand; Phosphorescence; Alkynyl complexes
资金
- Region Bretagne, France
- Conseil Departemental des Cotes d'Armor, France
A series of luminescent chloro- and alkynyl-platinum (II) complexes with tridentate cyclometalated ligands have been synthesized and characterized, with their electrochemical and luminescent properties investigated. The electron-withdrawing groups on the alkynyl ligands can induce a red shift in the emission band. This study provides insights into the structure-property relationship of these complexes in terms of their luminescence.
A series of luminescent chloro- and alkynyl-platinum (II) complexes containing various tridentate cyclometalated ligands derived from phenyl-pyridin-2-ylpyrimidine and alkynyl ligands has been successfully synthesized and characterized. Their electrochemical, electronic absorption and luminescence properties have been experimentally investigated and supported by (Time-Dependent) Density Functional Theory ((TD)-DFT) calculations. Electrochemical studies show the presence of a ligand-centered reduction originating from the cyclometalating NNC ligands, as well as a major ligand-centered oxidation process (NNC or alkynyl) with minor contributions of the metal. Most of the complexes exhibits yellow-to-red luminescence at room-temperature in diluted solutions, in frozen matrices and in the solid state. Electron-withdrawing groups on the alkynyl-ligand induce a red shift of the emission band with increased quantum yield in solution. The emission is also sensitive to the position of the pyridyl fragment on the pyrimidine core: complexes with electron-poorer 4-pyridin-2-ylpyrimidine ligands exhibit red-shifted emission and decreased quantum yield compared to their 2-pyridin-4yl analogues. In solid state, chloro-platinum complexes without tBu bulky group exhibit red-shifted excimer emission.
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