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Halogen Bonding to Amplify Luminescence: A Case Study Using a Platinum Cyclometalated Complex
Author(s) -
Sivchik Vasily V.,
Solomatina Anastasia I.,
Chen YiTing,
Karttunen Antti J.,
Tunik Sergey P.,
Chou PiTai,
Koshevoy Igor O.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201507229
Subject(s) - luminescence , chemistry , chromophore , platinum , halogen , quantum yield , pyridine , halogen bond , photochemistry , crystallography , fluorescence , materials science , catalysis , optoelectronics , medicinal chemistry , organic chemistry , alkyl , physics , quantum mechanics
The cocrystallization of a weakly luminescent platinum complex [Pt(btpy)(PPh 3 )Cl] ( 1 ) (Hbtpy=2‐(2benzothienyl)pyridine; emission quantum yield Φ em =0.03) with fluorinated bromo‐ and iodoarenes C 6 F 6‐ n X n (X=Br, I; n =1, 2) results in the formation of efficient halogen‐bonding (XB) interactions PtCl⋅⋅⋅XR. An up to 22‐fold enhancement ( Φ em =0.65) in the luminescence intensity of the cocrystallized compound is detected, without a substantial change of the emission energy. Based on crystallographic, photophysical, and theoretical investigations, the contribution of the XB donors C 6 F 6‐ n X n to the amplification of luminescence intensity is attributed to the enhancement of spin–orbit coupling through the heavy‐atom effect, and simultaneously to the suppression of the nonradiative relaxation pathways by increasing the rigidity of the chromophore center.