Conjugated-linker dependence of the photophysical properties and electronic structure of chlorin dyads

Kang, Hyun Suk; Satraitis, Andrius; Meares, Adam; Bhagavathy, Ganga Viswanathan; Diers, James R.; Niedzwiedzki, Dariusz M.; Kirmaier, Christine; Ptaszek, Marcin; Bocian, David F.; Holten, Dewey

doi:10.1142/s1088424621500620

Conjugated-linker dependence of the photophysical properties and electronic structure of chlorin dyads

Journal Article · Thu May 27 00:00:00 EDT 2021 · Journal of Porphyrins and Phthalocyanines

DOI:https://doi.org/10.1142/s1088424621500620· OSTI ID:1830810

Kang, Hyun Suk ^[1]; Satraitis, Andrius ^[2]; Meares, Adam ^[2]; Bhagavathy, Ganga Viswanathan ^[2]; Diers, James R. ^[3]; Niedzwiedzki, Dariusz M. ^[4]; Kirmaier, Christine ^[4]; Ptaszek, Marcin ^[2]; Bocian, David F. ^[3]; Holten, Dewey ^[4]

Washington Univ., St. Louis, MO (United States); Washington University
Univ. of Maryland Baltimore County (UMBC), Baltimore, MD (United States)
Univ. of California, Riverside, CA (United States)
Washington Univ., St. Louis, MO (United States)

The synthesis, photophysical properties and electronic structure of seven new chlorin dyads and associated benchmark monomers are described. Each dyad contains two identical chlorins linked at the macrocycle β-pyrrole 13-position. The extent of electronic communication between chlorin constituents depends on the nature of the conjugated linker. The communication is assessed by modification of prominent ground-state absorption and redox properties, rate constants and yields of excited-state decay processes, and molecular-orbital characteristics. Relative to the benchmark monomers, the chlorin dyads in toluene exhibit a substantial bathochromic shift of the long-wavelength absorption band (30 nm average), two-fold increased radiative rate constant [average (10 ns)^-1vs. (22 ns)^-1], reduced singlet excited-state lifetimes (average 5.0 ns vs. 8.2 ns), and increased fluorescence quantum yields (average 0.56 vs. 0.42). The excited-state lifetime and fluorescence yield for the chlorin dyad with a benzothiadiazole linker are reduced substantially in benzonitrile vs. toluene due largely to ~25-fold accelerated internal conversion. The results aid design strategies for molecular architectures that may find utility in solar-energy conversion and photomedicine.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: FG02-05ER15661

OSTI ID:: 1830810

Journal Information:: Journal of Porphyrins and Phthalocyanines, Journal Name: Journal of Porphyrins and Phthalocyanines Journal Issue: 07n08 Vol. 25; ISSN 1088-4246

Publisher:: World ScientificCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chlorin dyads
conjugated linkers
electronic communication
excited-state dynamics
orbital splitting

Conjugated-linker dependence of the photophysical properties and electronic structure of chlorin dyads

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