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Substituent control of the ultrafast twisted intramolecular charge transfer rate in dimethylaminochalcone derivatives

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Abstract

The effect of acceptor strength variation on ultrafast twisting relaxation dynamics was investigated by comparing the ultrafast relaxation dynamics in a series of dimethylaminochalcone (DMAC) derivatives. Employing femtosecond resolved transient absorption and fluorescence experiments, the twisted intramolecular charge transfer (TICT) relaxation rate is shown to vary from 2.0 picoseconds in a weak electron accepting system to 420 femtoseconds in a strong electron accepting system. The strength of the acceptor, empirically expressed as Hammett's constant, is shown to exhibit a linear free energy relationship (LFER) with the twisting rate. It is proposed that variation in the charge pulling capacity of the acceptor modifies the torsional barrier along the TICT coordinate in the S1 state, resulting in a tunable TICT relaxation rate, depending on the acceptor strength.

Graphical abstract: Substituent control of the ultrafast twisted intramolecular charge transfer rate in dimethylaminochalcone derivatives

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Publication details

The article was received on 08 Dec 2017, accepted on 06 Feb 2018 and first published on 06 Feb 2018


Article type: Paper
DOI: 10.1039/C7CP08239H
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
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    Substituent control of the ultrafast twisted intramolecular charge transfer rate in dimethylaminochalcone derivatives

    R. Ghosh, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C7CP08239H

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