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Title: 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 (B y and B x) bands of typical porphyrins into the green, red and near-infrared (Q x and Q y) 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 S 1 state with bacteriochlorin-like properties, including a 1-5 ns lifetime.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Washington Univ., St. Louis, MO (United States). Dept. of Chemistry
  2. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  3. North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry
  4. 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) (SC-22)
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. 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., and Holten, Dewey. Mon . "Origin of Panchromaticity in Multichromophore–Tetrapyrrole Arrays". United States. doi: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},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 36,
volume = 122,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

Annulated bacteriochlorins for near-infrared photophysical studies
journal, January 2019

  • Fujita, Hikaru; Jing, Haoyu; Krayer, Michael
  • New Journal of Chemistry, Vol. 43, Issue 19
  • DOI: 10.1039/c9nj01113g

A bacteriochlorin-diketopyrrolopyrrole triad as a donor for solution-processed bulk heterojunction organic solar cells
journal, January 2019

  • Ponsot, Flavien; Bucher, Léo; Desbois, Nicolas
  • Journal of Materials Chemistry C, Vol. 7, Issue 31
  • DOI: 10.1039/c9tc02724f

Annulated bacteriochlorins for near-infrared photophysical studies
journal, January 2019

  • Fujita, Hikaru; Jing, Haoyu; Krayer, Michael
  • New Journal of Chemistry, Vol. 43, Issue 19
  • DOI: 10.1039/c9nj01113g

A bacteriochlorin-diketopyrrolopyrrole triad as a donor for solution-processed bulk heterojunction organic solar cells
journal, January 2019

  • Ponsot, Flavien; Bucher, Léo; Desbois, Nicolas
  • Journal of Materials Chemistry C, Vol. 7, Issue 31
  • DOI: 10.1039/c9tc02724f