Electronic Structure and Excited-State Dynamics of Rylene–Tetrapyrrole Panchromatic Absorbers

Rong, Jie; Magdaong, Nikki Cecil M.; Taniguchi, Masahiko; Diers, James R.; Niedzwiedzki, Dariusz M.; Kirmaier, Christine; Lindsey, Jonathan S.; Bocian, David F.; Holten, Dewey

doi:10.1021/acs.jpca.1c05771

Title: Electronic Structure and Excited-State Dynamics of Rylene–Tetrapyrrole Panchromatic Absorbers

Journal Article · Thu Sep 02 00:00:00 EDT 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.1c05771· OSTI ID:1830802

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North Carolina State Univ., Raleigh, NC (United States)
Washington Univ., St. Louis, MO (United States)
Univ. of California, Riverside, CA (United States)

Panchromatic absorbers have potential applications in molecular-based energy-conversion schemes. A prior porphyrin–perylene dyad (P-PMI, where “MI” denotes monoimide) coupled via an ethyne linker exhibits panchromatic absorption (350–700 nm) and a tetrapyrrole-like lowest singlet excited state with a relatively long singlet excited-state lifetime (τ_S) and increased fluorescence quantum yield (Φ_f) versus the parent porphyrin. To explore the extension of panchromaticity to longer wavelengths, three arrays have been synthesized: a chlorin–terrylene dyad (C-TMI), a bacteriochlorin–terrylene dyad (B-TMI), and a perylene–porphyrin–terrylene triad (PMI-P-TMI), where the terrylene, a π-extended homologue of perylene, is attached via an ethyne linker. Characterization of the spectra (absorption and fluorescence), excited-state properties (lifetime, yields, and rate constants of decay pathways), and molecular-orbital characteristics reveals unexpected subtleties. The wavelength of the red-region absorption band increases in the order C-TMI (705 nm) < PMI-P-TMI (749 nm) < B-TMI (774 nm), yet each array exhibits diminished Φ_f and shortened τ_S values. The PMI-P-TMI triad in toluene exhibits Φ_f = 0.038 and τ_S = 139 ps versus the all-perylene triad (PMI-P-PMI) for which Φ_f = 0.26 and τ_S = 2000 ps. The results highlight design constraints for auxiliary pigments with tetrapyrroles to achieve panchromatic absorption with retention of viable excited-state properties.

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Research Organization:: Washington Univ., St. Louis, MO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15661; SC0001035

OSTI ID:: 1830802

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 125, Issue 36; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hydrocarbons
Absorption
Fluorescence
Pyrroles
Aromatic compounds

Title: Electronic Structure and Excited-State Dynamics of Rylene–Tetrapyrrole Panchromatic Absorbers

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