Understanding the influence of geometric and electronic structure on the excited state dynamical and photoredox properties of perinone chromophores

Literature Information

Publication Date 2021-10-14
DOI 10.1039/D1CP03870B
Impact Factor 3.676
Authors

Kaylee A. Wells, Jonathan R. Palmer, Sofia Garakyaraghi, Joseph M. Favale, Mary Katharine Valchar, Arnab Chakraborty, Felix N. Castellano


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Abstract

In this work, a series of eight similarly structured perinone chromophores were synthesized and photophysically characterized to elucidate the electronic and structural tunability of their excited state properties, including excited state redox potentials and fluorescence lifetimes/quantum yields. Despite their similar structure, these chromophores exhibited a broad range of visible absorption properties, quantum yields, and excited state lifetimes. In conjunction with static and time-resolved spectroscopies from the ultrafast to nanosecond time regimes, time-dependent computational modeling was used to correlate this behavior to the relationship between non-radiative decay and the energy-gap law. Additionally, the ground and excited state redox potentials were calculated and found to be tunable over a range of 1 V depending on the diamine or anhydride used in their synthesis (Ered* = 0.45–1.55 V; Eox* = −0.88 to −1.67 V), which is difficult to achieve with typical photoredox-active transition metal complexes. These diverse chromophores can be easily prepared, and with their range of photophysical tunability, will be valuable for future use in photofunctional applications.

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Contents

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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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