Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO2 Photoreduction

Streater, Daniel H.; Kennehan, Eric R.; Wang, Denan; Fiankor, Christian; Chen, Liangji; Yang, Chongqing; Li, Bo; Liu, Daohua; Ibrahim, Faysal; Hermans, Ive; Kohlstedt, Kevin L.; Luo, Long; Zhang, Jian; Huang, Jier

doi:10.1021/jacs.3c10627

Title: Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO₂ Photoreduction

Journal Article · 06 February 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c10627 · OSTI ID:2335686

Streater, Daniel H. ^[1]; Kennehan, Eric R. ^[2];

^[3];

^[4]; Chen, Liangji ^[3]; Yang, Chongqing ^[5]; Li, Bo ^[3]; Liu, Daohua ^[6];

^[7];

^[8];

^[6];

^[5];

^[9]

Marquette University, Milwaukee, WI (United States); Boston College
Magnitude Instruments, State College, PA (United States)
Boston College, Chestnut Hill, MA (United States)
University of Nebraska-Lincoln, NE (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Wayne State University, Detroit, MI (United States)
University of Wisconsin-Madison, WI (United States)
Northwestern University, Evanston, IL (United States)
Marquette University, Milwaukee, WI (United States); Boston College, Chestnut Hill, MA (United States)

Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO₂ reduction performance after incorporating a Re(bpy)(CO)₃Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF). These interactions ultimately lead the Re-f-COF isomer to function as an efficient CO₂ reduction photocatalyst, while the Re-r-COF isomer shows minimal photocatalytic activity. Furthermore, these findings not only reveal the essential role linker chemistry plays in COF photophysical and photocatalytic properties but also offer a unique opportunity to design photosensitizers that can selectively direct charges.

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Research Organization:: Boston College, Chestnut Hill, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0024049; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 2335686

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 7 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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14 SOLAR ENERGY
Bipyridine
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Excited states
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CCDC 2311631: Experimental Crystal Structure Determination H., Streater, Daniel; R., Kennehan, Eric; Denan, Wang, https://doi.org/10.5517/ccdc.csd.cc2hlfr9 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2311632: Experimental Crystal Structure Determination H., Streater, Daniel; R., Kennehan, Eric; Denan, Wang, https://doi.org/10.5517/ccdc.csd.cc2hlfsb The current record is supplemented by this dataset	dataset	January 2024

Title: Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO2 Photoreduction

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Title: Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO₂ Photoreduction