Fluorescence quantum yield rationalized by the magnitude of the charge transfer in π-conjugated terpyridine derivatives
文献信息
Marie Humbert-Droz, Claude Piguet, Tomasz A. Wesolowski
Terpyridine derivatives are of great interest due to their unique photophysical properties when used as antennas in metallic complexes. Several experimental and theoretical studies indicate strong charge-transfer character of the lowest electronic excited state, which could be exploited for predicting fluorescence quantum yields from the magnitude of the charge separation induced by electronic transitions. Focusing on substituted 4′-phenyl-2,2′:6′2′′-terpyridyl, we report on two measures of the charge separation obtained from high-level calculations in ground and excited states (length of the change of the dipole moment and the electron–hole distance). Our refined model confirms that the fluorescence quantum yield shows a global S-shape dependence on the magnitude of the charge separation, which can be quantified either by the change in dipole moments between the ground and excited states or by the associated charge–hole distances. This approach provides a remarkable tool for the molecular design of a fluorescent polyaromatic antenna.
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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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