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Long‐Lived Circularly Polarized Phosphorescence in Helicene‐NHC Rhenium(I) Complexes: The Influence of Helicene, Halogen, and Stereochemistry on Emission Properties
Author(s) -
Gauthier Etienne S.,
Abella Laura,
Hellou Nora,
Darquié Benoît,
Caytan Elsa,
Roisnel Thierry,
Vanthuyne Nicolas,
Favereau Ludovic,
SrebroHooper Monika,
Williams J. A. Gareth,
Autschbach Jochen,
Crassous Jeanne
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202002387
Subject(s) - helicene , phosphorescence , enantiopure drug , chemistry , halogen , rhenium , photochemistry , carbene , quantum yield , luminescence , stereochemistry , crystallography , fluorescence , molecule , materials science , organic chemistry , enantioselective synthesis , physics , alkyl , catalysis , optoelectronics , quantum mechanics
The first enantiopure chiral‐at‐rhenium complexes of the form fac ‐ReX(CO) 3 (:C^N) have been prepared, where :C^N is a helicene‐N‐heterocyclic carbene (NHC) ligand and X=Cl or I. These have complexes show strong changes in the emission characteristics, notably strongly enhanced phosphorescence lifetimes (reaching 0.7 ms) and increased circularly polarized emission (CPL) activity, as compared to their parent chiral models lacking the helicene unit. The halogen along with its position within the dissymmetric stereochemical environment strongly affect the photophysics of the complexes, particularly the phosphorescence quantum yield and lifetime. These results give fresh insight into fine tuning of photophysical and chiroptical properties of Re‐NHC systems.