Photophysical Properties and Electronic Structure of Porphyrins Bearing Zero to Four meso-Phenyl Substituents: New Insights into Seemingly Well Understood Tetrapyrroles
Abstract
Six free base porphyrins bearing 0–4 meso substituents have been examined by steady-state and time-resolved absorption and fluorescence spectroscopy in both toluene and N,N-dimethylformamide (DMF). The lifetime of the lowest singlet excited state (S1) decreases with an increase in the number of meso-phenyl groups; the values in toluene are H2P-0 (15.5 ns) > H2P-1 (14.9 ns) > H2P-2c (14.4 ns) > H2P-2t (13.8 ns) ~ H2P-3 (13.8 ns) > H2P-4 (12.8 ns), where “H2P” refers to the core free base porphyrin, the numerical suffix indicates the number of meso-phenyl groups, and “c” and “t” refer to cis and trans, respectively. The opposite trend is found for the fluorescence quantum yield; the values in toluene are H2P-0 (0.049) < H2P-1 (0.063) ~ H2P-2c (0.063) < H2P-2t (0.071) < H2P-3 (0.073) < H2P-4 (0.090). Similar trends occur in DMF. All radiative and non-radiative (internal conversion and intersystem crossing) rate constants for S1 decay increase with increasing number of meso-phenyl groups. The increase in the rate constant for fluorescence parallels an increase in oscillator strength of the So → S1 absorption manifold. Here, the trend is reproduced by time-dependent density functional theory calculations. The calculations within the context of the four-orbital model revealmore »
- Authors:
-
- Washington Univ., St. Louis, MO (United States)
- North Carolina State Univ., Raleigh, NC (United States)
- Univ. of California, Riverside, CA (United States)
- Publication Date:
- Research Org.:
- Washington Univ., St. Louis, MO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1774947
- Grant/Contract Number:
- FG02-05ER15651
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 49; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; Hydrocarbons; Aromatic compounds; Energy; Absorption; Pyrroles
Citation Formats
Mandal, Amit Kumar, Taniguchi, Masahiko, Diers, James R., Niedzwiedzki, Dariusz M., Kirmaier, Christine, Lindsey, Jonathan S., Bocian, David F., and Holten, Dewey. Photophysical Properties and Electronic Structure of Porphyrins Bearing Zero to Four meso-Phenyl Substituents: New Insights into Seemingly Well Understood Tetrapyrroles. United States: N. p., 2016.
Web. doi:10.1021/acs.jpca.6b09483.
Mandal, Amit Kumar, Taniguchi, Masahiko, Diers, James R., Niedzwiedzki, Dariusz M., Kirmaier, Christine, Lindsey, Jonathan S., Bocian, David F., & Holten, Dewey. Photophysical Properties and Electronic Structure of Porphyrins Bearing Zero to Four meso-Phenyl Substituents: New Insights into Seemingly Well Understood Tetrapyrroles. United States. https://doi.org/10.1021/acs.jpca.6b09483
Mandal, Amit Kumar, Taniguchi, Masahiko, Diers, James R., Niedzwiedzki, Dariusz M., Kirmaier, Christine, Lindsey, Jonathan S., Bocian, David F., and Holten, Dewey. Tue .
"Photophysical Properties and Electronic Structure of Porphyrins Bearing Zero to Four meso-Phenyl Substituents: New Insights into Seemingly Well Understood Tetrapyrroles". United States. https://doi.org/10.1021/acs.jpca.6b09483. https://www.osti.gov/servlets/purl/1774947.
@article{osti_1774947,
title = {Photophysical Properties and Electronic Structure of Porphyrins Bearing Zero to Four meso-Phenyl Substituents: New Insights into Seemingly Well Understood Tetrapyrroles},
author = {Mandal, Amit Kumar and Taniguchi, Masahiko and Diers, James R. and Niedzwiedzki, Dariusz M. and Kirmaier, Christine and Lindsey, Jonathan S. and Bocian, David F. and Holten, Dewey},
abstractNote = {Six free base porphyrins bearing 0–4 meso substituents have been examined by steady-state and time-resolved absorption and fluorescence spectroscopy in both toluene and N,N-dimethylformamide (DMF). The lifetime of the lowest singlet excited state (S1) decreases with an increase in the number of meso-phenyl groups; the values in toluene are H2P-0 (15.5 ns) > H2P-1 (14.9 ns) > H2P-2c (14.4 ns) > H2P-2t (13.8 ns) ~ H2P-3 (13.8 ns) > H2P-4 (12.8 ns), where “H2P” refers to the core free base porphyrin, the numerical suffix indicates the number of meso-phenyl groups, and “c” and “t” refer to cis and trans, respectively. The opposite trend is found for the fluorescence quantum yield; the values in toluene are H2P-0 (0.049) < H2P-1 (0.063) ~ H2P-2c (0.063) < H2P-2t (0.071) < H2P-3 (0.073) < H2P-4 (0.090). Similar trends occur in DMF. All radiative and non-radiative (internal conversion and intersystem crossing) rate constants for S1 decay increase with increasing number of meso-phenyl groups. The increase in the rate constant for fluorescence parallels an increase in oscillator strength of the So → S1 absorption manifold. Here, the trend is reproduced by time-dependent density functional theory calculations. The calculations within the context of the four-orbital model reveal that the enhanced So → S1 radiative probabilities derive from a preferential effect of the meso-phenyl groups to raise the energy of the highest occupied molecular orbital, which underpins a parallel bathochromic shift in the So → S1 absorption wavelength. Polarizations of the S1 and S2 excited states with respect to molecular structural features (e.g., the central proton axis) are analyzed in the context of historical conventions for porphyrins versus chlorins and bacteriochlorins, where some ambiguity exists, including for porphine, one of the simplest tetrapyrroles. Collectively, the study affords fundamental insights into the photophysical properties and electronic structure of meso-phenylporphyrins that should aid their continued widespread use as benchmarks for tetrapyrrole-based architectures in chemical, solar-energy and life-sciences research.},
doi = {10.1021/acs.jpca.6b09483},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 49,
volume = 120,
place = {United States},
year = {Tue Dec 06 00:00:00 EST 2016},
month = {Tue Dec 06 00:00:00 EST 2016}
}
Web of Science
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