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Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes
Author(s) -
Saleh Nidal,
Moore Barry,
Srebro Monika,
Vanthuyne Nicolas,
Toupet Loïc,
Williams J. A. Gareth,
Roussel Christian,
Deol Kirandeep K.,
Muller Gilles,
Autschbach Jochen,
Crassous Jeanne
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405176
Subject(s) - helicene , bathochromic shift , protonation , circular dichroism , chemistry , luminescence , photochemistry , homo/lumo , crystallography , fluorescence , materials science , molecule , organic chemistry , physics , optoelectronics , ion , quantum mechanics
Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a . Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation.