Tuning the Electronic Structure and Properties of Perylene–Porphyrin–Perylene Panchromatic Absorbers

Amanpour, Javad; Hu, Gongfang; Alexy, Eric J.; Mandal, Amit Kumar; Kang, Hyun Suk; Yuen, Jonathan M.; Diers, James R.; Bocian, David F.; Lindsey, Jonathan S.; Holten, Dewey

doi:10.1021/acs.jpca.6b06857

Title: Tuning the Electronic Structure and Properties of Perylene–Porphyrin–Perylene Panchromatic Absorbers

Journal Article · Fri Sep 16 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b06857· OSTI ID:1774948

Amanpour, Javad ^[1]; Hu, Gongfang ^[1]; Alexy, Eric J. ^[1]; Mandal, Amit Kumar ^[2]; Kang, Hyun Suk ^[2]; Yuen, Jonathan M. ^[2]; Diers, James R. ^[3]; Bocian, David F. ^[3]; Lindsey, Jonathan S. ^[1]; Holten, Dewey ^[2]

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

Light-harvesting architectures that afford strong absorption across the near-ultraviolet to near-infrared region, namely panchromatic absorptivity, are potentially valuable for capturing the broad spectral distribution of sunlight. One previously reported triad consisting of two perylene monoimides strongly coupled to a free base porphyrin via ethyne linkers (FbT) shows panchromatic absorption together with a porphyrin-like S1 excited state albeit at lower energy than that of a typical monomeric porphyrin. Here, two new porphyrin–bis(perylene) triads have been prepared wherein the porphyrin bears two pentafluorophenyl substituents. The porphyrin is in the free base (FbT-F) or zinc chelate (ZnT-F) forms. The zinc chelate (ZnT) of the original triad bearing non-fluorinated aryl rings also was prepared. The triads were characterized using static and time-resolved optical spectroscopy. The results were analyzed with the aid of molecular-orbital characteristics obtained using density functional theory calculations. Of the four triads, FbT is the most panchromatic in affording the most even distribution of spectral intensity as well exhibiting the largest wavelength span (380-750 nm). The triads exhibit fluorescence yields (0.35 for FbT-F in toluene) that are substantially greater than for the porphyrin benchmarks (0.049 for FbP-F). The singlet excited-state lifetimes (τ_S) for the triads in toluene decrease in the order FbT-F (2.7 ns) > FbT (2.0 ns) > ZnT (1.2 ns) ~ ZnT-F (1.1 ns). The τ_S values in benzonitrile are FbT (1.3 ns) > FbT-F (1.2 ns) > ZnT-F (0.6 ns) > ZnT (0.2 ns). Furthermore, the free base triads exhibit relatively long (1.2-2.7 ns) excited-state lifetimes in both polar and nonpolar media. The combined photophysical characteristics indicate that FbT and FbT-F are the best choices for panchromatic light-harvesting systems. Collectively, the findings afford insights into the effects of electronic structure on the panchromatic behavior of ethynyl-linked porphyrin–perylene architectures that can help guide next-generation designs and utilization of these systems.

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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

OSTI ID:: 1774948

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 38; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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