Substituent control of the ultrafast twisted intramolecular charge transfer rate in dimethylaminochalcone derivatives
Literature Information
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.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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