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Air‐Stable Blue Phosphorescent Tetradentate Platinum(II) Complexes as Strong Photo‐Reductant
Author(s) -
Li Kai,
Wan Qingyun,
Yang Chen,
Chang XiaoYong,
Low KamHung,
Che ChiMing
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201808642
Subject(s) - phosphorescence , chemistry , photochemistry , redox , aryl , platinum , electrochemistry , excited state , halide , reductive elimination , inorganic chemistry , catalysis , fluorescence , organic chemistry , electrode , alkyl , physics , quantum mechanics , nuclear physics
Strong photo‐reductants have applications in photo‐redox organic synthesis involving reductive activation of C−X(halide) and C=O bonds. We report herein air‐stable Pt II complexes supported by tetradentate bis(phenolate‐NHC) ligands having peripheral electron‐donating N ‐carbazolyl groups. Photo‐physical, electrochemical, and computational studies reveal that the presence of N ‐carbazolyl groups enhances the light absorption and redox reversibility because of its involvement into the frontier MOs in both ground and excited states, making the complexes robust strong photo‐reductant with E ([Pt] +/ *) over −2.6 V vs. Cp 2 Fe +/0 . The one‐electron reduced [Pt] − species are stronger reductants with E PC ([Pt] 0/− ) up to −3.1 V vs. Cp 2 Fe +/0 . By virtue of the strong reducing nature of these species generated upon light excitation, they can be used in light‐driven reductive coupling of carbonyl compounds and reductive debromination of a wide range of unactivated aryl bromides.