Effects of Strong Electronic Coupling in Chlorin and Bacteriochlorin Dyads

The Journal of Physical Chemistry. a
Hyun Suk KangDavid F Bocian

Abstract

Achieving tunable, intense near-infrared absorption in molecular architectures with properties suitable for solar light harvesting and biomedical studies is of fundamental interest. Herein, we report the photophysical, redox, and molecular-orbital characteristics of nine hydroporphyrin dyads and associated benchmark monomers that have been designed and synthesized to attain enhanced light harvesting. Each dyad contains two identical hydroporphyrins (chlorin or bacteriochlorin) connected by a linker (ethynyl or butadiynyl) at the macrocycle β-pyrrole (3- or 13-) or meso (15-) positions. The strong electronic communication between constituent chromophores is indicated by the doubling of prominent absorption features, split redox waves, and paired linear combinations of frontier molecular orbitals. Relative to the benchmarks, the chlorin dyads in toluene show substantial bathochromic shifts of the long-wavelength absorption band (17-31 nm), modestly reduced singlet excited-state lifetimes (τS = 3.6-6.2 ns vs 8.8-12.3 ns), and increased fluorescence quantum yields (Φf = 0.37-0.57 vs 0.34-0.39). The bacteriochlorin dyads in toluene show significant bathochromic shifts (25-57 nm) and modestly reduced τS (1.6-3.4 ns vs 3.5-5.3 ns) and...Continue Reading

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Citations

Apr 20, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Muthyala Nagarjuna ReddyJonathan S Lindsey
Jan 2, 2020·Proceedings of the National Academy of Sciences of the United States of America·Philip D LaibleChristine Kirmaier
Aug 29, 2018·The Journal of Physical Chemistry. a·Jonathan M YuenDewey Holten
Jul 24, 2018·The Journal of Organic Chemistry·Adam MearesMarcin Ptaszek
Sep 3, 2021·The Journal of Physical Chemistry. a·Jie RongDewey Holten

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