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Title: Synthesis of arrays containing porphyrin, chlorin, and perylene-imide constituents for panchromatic light-harvesting and charge separation

Abstract

Achieving solar light harvesting followed by efficient charge separation and transport is an essential objective of molecular-based artificial photosynthesis. Architectures that afford strong absorption across the near-UV to near-infrared region, namely panchromatic absorptivity, are critically important given the broad spectral distribution of sunlight. A tetrapyrrole–perylene pentad array was synthesized and investigated as a means to integrate panchromatic light harvesting and intramolecular charge separation. The pentad consists of three moieties: (1) a panchromatically absorbing triad, in which a porphyrin is strongly coupled to two perylene-monoimides via ethyne linkages; (2) a perylene-diimide electron acceptor; and (3) a chlorin hole-trapping unit. Integrating the three components with diphenylethyne linkers generates moderate electronic coupling for intramolecular energy and hole/electron transfer. The construction of the array relies on a stepwise strategy for incorporating modular pigment building blocks. The key building blocks include a trans-A 2BC porphyrin, a chlorin, a perylene-monoimide, and a perylene-diimide, each bearing appropriate (halo, ethynyl) synthetic handles for Pd-catalyzed Sonogashira coupling reactions. One target pentad, three tetrads, four triads, and four monomeric benchmark compounds were synthesized from six building blocks (three new, three reported) and 10 new synthetic intermediates. Four of the tetrapyrrole-containing arrays are zinc chelated, and four others are in themore » free base form. Absorption and fluorescence spectra and fluorescence quantum yields were also measured. Collectively, investigations of the arrays reveal insights into principles for the design of novel reaction centers integrated with a panchromatic antenna for artificial photosynthetic studies.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, North Carolina State University, Raleigh, USA
  2. Department of Chemistry, Washington University, St. Louis, USA
  3. Department of Chemistry, University of California, Riverside, USA
Publication Date:
Research Org.:
Washington Univ., St. Louis, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1457803
Alternate Identifier(s):
OSTI ID: 1540073
Grant/Contract Number:  
FG02-05ER15661
Resource Type:
Journal Article: Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 8 Journal Issue: 42; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Hu, Gongfang, Kang, Hyun Suk, Mandal, Amit Kumar, Roy, Arpita, Kirmaier, Christine, Bocian, David F., Holten, Dewey, and Lindsey, Jonathan S. Synthesis of arrays containing porphyrin, chlorin, and perylene-imide constituents for panchromatic light-harvesting and charge separation. United Kingdom: N. p., 2018. Web. doi:10.1039/C8RA04052D.
Hu, Gongfang, Kang, Hyun Suk, Mandal, Amit Kumar, Roy, Arpita, Kirmaier, Christine, Bocian, David F., Holten, Dewey, & Lindsey, Jonathan S. Synthesis of arrays containing porphyrin, chlorin, and perylene-imide constituents for panchromatic light-harvesting and charge separation. United Kingdom. doi:10.1039/C8RA04052D.
Hu, Gongfang, Kang, Hyun Suk, Mandal, Amit Kumar, Roy, Arpita, Kirmaier, Christine, Bocian, David F., Holten, Dewey, and Lindsey, Jonathan S. Mon . "Synthesis of arrays containing porphyrin, chlorin, and perylene-imide constituents for panchromatic light-harvesting and charge separation". United Kingdom. doi:10.1039/C8RA04052D.
@article{osti_1457803,
title = {Synthesis of arrays containing porphyrin, chlorin, and perylene-imide constituents for panchromatic light-harvesting and charge separation},
author = {Hu, Gongfang and Kang, Hyun Suk and Mandal, Amit Kumar and Roy, Arpita and Kirmaier, Christine and Bocian, David F. and Holten, Dewey and Lindsey, Jonathan S.},
abstractNote = {Achieving solar light harvesting followed by efficient charge separation and transport is an essential objective of molecular-based artificial photosynthesis. Architectures that afford strong absorption across the near-UV to near-infrared region, namely panchromatic absorptivity, are critically important given the broad spectral distribution of sunlight. A tetrapyrrole–perylene pentad array was synthesized and investigated as a means to integrate panchromatic light harvesting and intramolecular charge separation. The pentad consists of three moieties: (1) a panchromatically absorbing triad, in which a porphyrin is strongly coupled to two perylene-monoimides via ethyne linkages; (2) a perylene-diimide electron acceptor; and (3) a chlorin hole-trapping unit. Integrating the three components with diphenylethyne linkers generates moderate electronic coupling for intramolecular energy and hole/electron transfer. The construction of the array relies on a stepwise strategy for incorporating modular pigment building blocks. The key building blocks include a trans-A2BC porphyrin, a chlorin, a perylene-monoimide, and a perylene-diimide, each bearing appropriate (halo, ethynyl) synthetic handles for Pd-catalyzed Sonogashira coupling reactions. One target pentad, three tetrads, four triads, and four monomeric benchmark compounds were synthesized from six building blocks (three new, three reported) and 10 new synthetic intermediates. Four of the tetrapyrrole-containing arrays are zinc chelated, and four others are in the free base form. Absorption and fluorescence spectra and fluorescence quantum yields were also measured. Collectively, investigations of the arrays reveal insights into principles for the design of novel reaction centers integrated with a panchromatic antenna for artificial photosynthetic studies.},
doi = {10.1039/C8RA04052D},
journal = {RSC Advances},
issn = {2046-2069},
number = 42,
volume = 8,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C8RA04052D

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