A peculiar dependence of intersystem crossing of p-nitro-2,5-distyrylfuran on the dielectric properties of the solvent

Literature Information

Publication Date 2011-10-17
DOI 10.1039/C1CP22450F
Impact Factor 3.676
Authors

B. Carlotti, F. Elisei, A. Spalletti


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Abstract

The excited state behaviour of EE-2-(4′-nitrostyryl),5-styryl-furan (NSF) has been studied with different stationary and pulsed spectrometric techniques in solvents of different polarity and polarizability. The interpretation of previous results on the fluorescence and intersystem crossing of NSF [Phys. Chem. Chem. Phys., 2011, 13, 4519] was found to be complicated by an uncommon effect of solvent polarity on the competitive relaxation pathways. To answer the open questions, the photobehaviour was revisited in solvents with a restricted range of the dielectric constant, also under conditions of constant polarizability, and in a large temperature range. The results thus obtained, supported by parallel quantum-mechanical calculations on the singlet/triplet properties, allowed a reasonable interpretation of the photobehaviour to be reached. This includes the role of an activated photoisomerization above room temperatures and the play of small changes of dielectric properties of the solvent in favouring ICT, thus affecting the efficiency of the ISC process, where an “inverse” energy gap trend was found to be operative.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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