Origin of Panchromaticity in Multichromophore–Tetrapyrrole Arrays
Abstract
Panchromatic absorbers that have robust photophysical properties enable new designs for molecular-based light-harvesting systems. Herein, we report experimental and theoretical studies of the spectral, redox, and excited-state properties of a series of perylene-monoimide–ethyne–porphyrin arrays wherein the number of perylene-monoimide units is stepped from one to four. In the arrays, a profound shift of absorption intensity from the strong violet-blue (By and Bx) bands of typical porphyrins into the green, red and near-infrared (Qx and Qy) regions stems from mixing of chromophore and tetrapyrrole molecular orbitals (MOs), which gives multiplets of MOs having electron density spread over the entire array. This reduces the extensive mixing between porphyrin excited-state configurations and the transition-dipole addition and subtraction that normally leads to intense B and weak Q bands. Reduced configurational mixing derives from moderate effects of the ethyne and perylene on the MO energies and a more substantial effect of electron-density delocalization to reduce the configuration-interaction energy. Quantitative oscillator-strength analysis shows that porphyrin intensity is also shifted into the perylene-like green-region absorption and that the ethyne linkers lend absorption intensity. The reduced porphyrin configurational mixing also endows the S1 state with bacteriochlorin-like properties, including a 1-5 ns lifetime.
- Authors:
-
- Washington Univ., St. Louis, MO (United States). Dept. of Chemistry
- Univ. of California, Riverside, CA (United States). Dept. of Chemistry
- North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry
- Washington Univ., St. Louis, MO (United States). Photosynthetic Antenna Research Center
- Publication Date:
- Research Org.:
- Washington Univ., St. Louis, MO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1471125
- Grant/Contract Number:
- FG02-05ER15661
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 36; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Yuen, Jonathan M., Diers, James R., Alexy, Eric J., Roy, Arpita, Mandal, Amit Kumar, Kang, Hyun Suk, Niedzwiedzki, Dariusz M., Kirmaier, Christine, Lindsey, Jonathan S., Bocian, David F., and Holten, Dewey. Origin of Panchromaticity in Multichromophore–Tetrapyrrole Arrays. United States: N. p., 2018.
Web. doi:10.1021/acs.jpca.8b06815.
Yuen, Jonathan M., Diers, James R., Alexy, Eric J., Roy, Arpita, Mandal, Amit Kumar, Kang, Hyun Suk, Niedzwiedzki, Dariusz M., Kirmaier, Christine, Lindsey, Jonathan S., Bocian, David F., & Holten, Dewey. Origin of Panchromaticity in Multichromophore–Tetrapyrrole Arrays. United States. https://doi.org/10.1021/acs.jpca.8b06815
Yuen, Jonathan M., Diers, James R., Alexy, Eric J., Roy, Arpita, Mandal, Amit Kumar, Kang, Hyun Suk, Niedzwiedzki, Dariusz M., Kirmaier, Christine, Lindsey, Jonathan S., Bocian, David F., and Holten, Dewey. 2018.
"Origin of Panchromaticity in Multichromophore–Tetrapyrrole Arrays". United States. https://doi.org/10.1021/acs.jpca.8b06815. https://www.osti.gov/servlets/purl/1471125.
@article{osti_1471125,
title = {Origin of Panchromaticity in Multichromophore–Tetrapyrrole Arrays},
author = {Yuen, Jonathan M. and Diers, James R. and Alexy, Eric J. and Roy, Arpita and Mandal, Amit Kumar and Kang, Hyun Suk and Niedzwiedzki, Dariusz M. and Kirmaier, Christine and Lindsey, Jonathan S. and Bocian, David F. and Holten, Dewey},
abstractNote = {Panchromatic absorbers that have robust photophysical properties enable new designs for molecular-based light-harvesting systems. Herein, we report experimental and theoretical studies of the spectral, redox, and excited-state properties of a series of perylene-monoimide–ethyne–porphyrin arrays wherein the number of perylene-monoimide units is stepped from one to four. In the arrays, a profound shift of absorption intensity from the strong violet-blue (By and Bx) bands of typical porphyrins into the green, red and near-infrared (Qx and Qy) regions stems from mixing of chromophore and tetrapyrrole molecular orbitals (MOs), which gives multiplets of MOs having electron density spread over the entire array. This reduces the extensive mixing between porphyrin excited-state configurations and the transition-dipole addition and subtraction that normally leads to intense B and weak Q bands. Reduced configurational mixing derives from moderate effects of the ethyne and perylene on the MO energies and a more substantial effect of electron-density delocalization to reduce the configuration-interaction energy. Quantitative oscillator-strength analysis shows that porphyrin intensity is also shifted into the perylene-like green-region absorption and that the ethyne linkers lend absorption intensity. The reduced porphyrin configurational mixing also endows the S1 state with bacteriochlorin-like properties, including a 1-5 ns lifetime.},
doi = {10.1021/acs.jpca.8b06815},
url = {https://www.osti.gov/biblio/1471125},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 36,
volume = 122,
place = {United States},
year = {Mon Aug 20 00:00:00 EDT 2018},
month = {Mon Aug 20 00:00:00 EDT 2018}
}
Web of Science
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