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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 (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:
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)
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}
}

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Cited by: 17 works
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Works referenced in this record:

Efficient Synthesis of Light-Harvesting Arrays Composed of Eight Porphyrins and One Phthalocyanine
journal, December 1999


A Tightly Coupled Linear Array of Perylene, Bis(Porphyrin), and Phthalocyanine Units that Functions as a Photoinduced Energy-Transfer Cascade
journal, October 2000


Towards Unimolecular Luminescent Solar Concentrators: Bodipy-Based Dendritic Energy-Transfer Cascade with Panchromatic Absorption and Monochromatized Emission
journal, September 2011


A strategy for the stepwise ring annulation of all four pyrrolic rings of a porphyrin
journal, January 2007


A metal-free “black dye” for panchromatic dye-sensitized solar cells
journal, January 2009


Doubly and Triply Linked Porphyrin−Perylene Monoimides as Near IR Dyes with Large Dipole Moments and High Photostability
journal, January 2011


Fused porphyrinoids as promising near-infrared absorbing dyes
journal, January 2013


Donor-π–Acceptor Based Stable Porphyrin Sensitizers for Dye-Sensitized Solar Cells: Effect of π-Conjugated Spacers
journal, March 2017


Engineering High-Potential Photo-oxidants with Panchromatic Absorption
journal, June 2017


Panchromatic Photosensitizers Based on Push-Pull, Unsymmetrically Substituted Porphyrazines
journal, December 2017


Ullazine Donor–π bridge‐Acceptor Organic Dyes for Dye‐Sensitized Solar Cells
journal, March 2018


Tuning the Electronic Structure and Properties of Perylene–Porphyrin–Perylene Panchromatic Absorbers
journal, September 2016


Tailoring Panchromatic Absorption and Excited-State Dynamics of Tetrapyrrole–Chromophore (Bodipy, Rylene) Arrays—Interplay of Orbital Mixing and Configuration Interaction
journal, November 2017


Panchromatic absorbers for solar light-harvesting
journal, January 2014


Some reactions of meso-formyloctaethylporhyrin
journal, January 1978


Meso-alkynyl porphyrins
journal, February 1992


Porphyrins in bio-inspired transformations: Light-harvesting to solar cell
journal, November 2012


Meso-Substituted Porphyrins for Dye-Sensitized Solar Cells
journal, November 2014


Porphyrin-Based Bulk Heterojunction Organic Photovoltaics: The Rise of the Colors of Life
journal, May 2015


β-Substituted Zn II porphyrins as dyes for DSSC: A possible approach to photovoltaic windows
journal, March 2018


Porphyrin-ethynyl arrays: Synthesis, design, and application
journal, July 2009


Conjugated porphyrin arrays: synthesis, properties and applications for functional materials
journal, January 2015


Design of diethynyl porphyrin derivatives with high near infrared fluorescence quantum yields
journal, January 2015


Effects of Strong Electronic Coupling in Chlorin and Bacteriochlorin Dyads
journal, January 2016


Single-Acetylene Linked Porphyrin Nanorings
journal, November 2017


Study of the Effects of Substitution on the Absorption Spectra of Porphin
journal, May 1959


Spectra of porphyrins
journal, January 1961


Natural transition orbitals
journal, March 2003


Effects of Substituents on Synthetic Analogs of Chlorophylls. Part 4: How Formyl Group Location Dictates the Spectral Properties of Chlorophylls b , d and f
journal, January 2015


Extending the Short and Long Wavelength Limits of Bacteriochlorin Near-Infrared Absorption via Dioxo- and Bisimide-Functionalization
journal, March 2015


Electronic Structure and Absorption Properties of Strongly Coupled Porphyrin–Perylene Arrays
journal, August 2015


Mesogenic Zinc(u) complexes of 5,10,15,20- tetraarylethynyl-substituted porphyrins
journal, April 1997


Magnesium Tetra(phenylethynyl)porphyrin: Stepwise Synthetic Route, Crystal Structures, and Longer Singlet Excited-State Lifetime than Zinc Congener
journal, September 2018


Works referencing / citing this record:

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


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