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A Step Beyond BRET: Fluorescence by Unbound Excitation from Luminescence FUEL
Published on: May 23, 2014
Excitation-Wavelength-Dependent Emission and Delayed Fluorescence in a Proton-Transfer System
Alexey S Berezin1, Katerina A Vinogradova1,2, Viktor P Krivopalov3
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk, 630090, Russia.
Abstract:
Manipulating the relaxation pathways of excited states and understanding mechanisms of photochemical reactions present important challenges in chemistry. Here we report a unique zinc(II) complex exhibiting unprecedented interplay between the excitation-wavelength-dependent emission, thermally activated delayed fluorescence (TADF) and excited state intramolecular proton transfer (ESIPT). The ESIPT process in the complex is favoured by a short intramolecular OH⋅⋅⋅N hydrogen bond. Synergy between the excitation-wavelength-dependent emission and ESIPT arises due to heavy zinc atom favouring intersystem crossing (isc). Reverse intersystem crossing (risc) and TADF are favoured by a narrow singlet-triplet gap, ΔEST ≈10 kJ mol-1 . These results provide the first insight into how a proton-transfer system can be modified to show a synergy between the excitation-wavelength-dependent emission, ESIPT and TADF. This strategy offers new perspectives for designing ESIPT and TADF emitters exhibiting tunable excitation-wavelength-dependent luminescence.
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