Display options
Cite
Amanpour J, Hu G, Alexy EJ, et al. Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers. J Phys Chem A. 2016;120(38):7434-50doi: 10.1021/acs.jpca.6b06857.
Amanpour, J., Hu, G., Alexy, E. J., Mandal, A. K., Kang, H. S., Yuen, J. M., Diers, J. R., Bocian, D. F., Lindsey, J. S., & Holten, D. (2016). Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers. The journal of physical chemistry. A, 120(38), 7434-50. https://doi.org/10.1021/acs.jpca.6b06857
Amanpour, Javad, et al. "Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers." The journal of physical chemistry. A vol. 120,38 (2016): 7434-50. doi: https://doi.org/10.1021/acs.jpca.6b06857
Amanpour J, Hu G, Alexy EJ, Mandal AK, Kang HS, Yuen JM, Diers JR, Bocian DF, Lindsey JS, Holten D. Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers. J Phys Chem A. 2016 Sep 29;120(38):7434-50. doi: 10.1021/acs.jpca.6b06857. Epub 2016 Sep 16. PMID: 27636001.
Copy Download .nbib Format: NLM
Share it on

J Phys Chem A. 2016 Sep 29;120(38):7434-50. doi: 10.1021/acs.jpca.6b06857. Epub 2016 Sep 16.

Tuning the Electronic Structure and Properties of Perylene-Porphyrin-Perylene Panchromatic Absorbers.

The journal of physical chemistry. A

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

Affiliations

  1. Department of Chemistry, North Carolina State University , Raleigh, North Carolina 27695-8204, United States.
  2. Department of Chemistry, Washington University , St. Louis, Missouri 63130-4889, United States.
  3. Department of Chemistry, University of California , Riverside, California 92521-0403, United States.

PMID: 27636001 DOI: 10.1021/acs.jpca.6b06857

Abstract

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 nonfluorinated 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 absorption spectral intensity as well as 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 (τS) 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 τS values in benzonitrile are FbT (1.3 ns) > FbT-F (1.2 ns) > ZnT-F (0.6 ns) > ZnT (0.2 ns). Thus, 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.

Publication Types