Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C60

Pratik, Saied Md; Gagliardi, Laura; Cramer, Christopher J.

doi:10.1021/acs.jpcc.9b10834

Title: Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C₆₀

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Abstract

Electronic structure calculations show that guest C60 in the porphyrin-containing metal organic frameworks Zn₂(TCPB)(DA-ZnP) (DA-MOF; H₄TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, DA-ZnP = [5,15-bis[(4-pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II)) and Zn₂(TCPB)(F-ZnP) (F-MOF; F-ZnP = [5,15-di(4-pyridyl)-10,20-bis(pentafluorophenyl)porphinato]zinc(II)) engenders high photoelectrical conductivity due to efficient donor–acceptor charge-transfer (CT) interactions. Structural modifications at the meso position of the porphyrin influence the preferred positions of C₆₀within the frameworks, giving rise to host–guest interactions with different anisotropic structural, electronic, and optoelectronic properties. A preferred slipped-parallel π-stacked interaction of C₆₀ that is predicted for NH₂-substituted DA-MOF and F-MOF fosters strong CT transitions and lowers band gaps by ~1.0 eV compared to the pristine DA-MOF and F-MOF. Hopping rates computed using Marcus theory are found to be anisotropic and accelerated by multiple orders of magnitude across π-stacked interfaces created by C₆₀ incorporation, a consequence of strong electronic coupling between initial and final diabatic states. Calculations indicate that photoinduced electron transfer, as well as direct CT from porphyrin to C₆₀ upon irradiation, triggers a charge separation process that leads to the formation of what should be long-lived electron-trapped states at the heterojunctions. Lastly, design principles revealed here for the control of photophysical and electron-transfer processes will be useful for constructing new MOF-derived visible- and infrared-based optoelectronics.

Authors:

^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., and Chemical Theory Center

Publication Date:: Thu Jan 23 00:00:00 EST 2020

Research Org.:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1714366

Grant/Contract Number:: SC0008688; FG02-17ER16362

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 124; Journal Issue: 3; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Charge transfer; Pyrroles; Metal organic frameworks; Chemical calculations; Electrical conductivity

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                    Pratik, Saied Md, Gagliardi, Laura, and Cramer, Christopher J. Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C60.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.jpcc.9b10834.

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                    Pratik, Saied Md, Gagliardi, Laura, & Cramer, Christopher J. Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C60.  United States.  https://doi.org/10.1021/acs.jpcc.9b10834

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                    Pratik, Saied Md, Gagliardi, Laura, and Cramer, Christopher J. Thu .  
"Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C60".  United States.  https://doi.org/10.1021/acs.jpcc.9b10834.  https://www.osti.gov/servlets/purl/1714366.

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@article{osti_1714366,

  title        = {Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C60},

  author       = {Pratik, Saied Md and Gagliardi, Laura and Cramer, Christopher J.},

  abstractNote = {Electronic structure calculations show that guest C60 in the porphyrin-containing metal organic frameworks Zn2(TCPB)(DA-ZnP) (DA-MOF; H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, DA-ZnP = [5,15-bis[(4-pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II)) and Zn2(TCPB)(F-ZnP) (F-MOF; F-ZnP = [5,15-di(4-pyridyl)-10,20-bis(pentafluorophenyl)porphinato]zinc(II)) engenders high photoelectrical conductivity due to efficient donor–acceptor charge-transfer (CT) interactions. Structural modifications at the meso position of the porphyrin influence the preferred positions of C60 within the frameworks, giving rise to host–guest interactions with different anisotropic structural, electronic, and optoelectronic properties. A preferred slipped-parallel π-stacked interaction of C60 that is predicted for NH2-substituted DA-MOF and F-MOF fosters strong CT transitions and lowers band gaps by ~1.0 eV compared to the pristine DA-MOF and F-MOF. Hopping rates computed using Marcus theory are found to be anisotropic and accelerated by multiple orders of magnitude across π-stacked interfaces created by C60 incorporation, a consequence of strong electronic coupling between initial and final diabatic states. Calculations indicate that photoinduced electron transfer, as well as direct CT from porphyrin to C60 upon irradiation, triggers a charge separation process that leads to the formation of what should be long-lived electron-trapped states at the heterojunctions. Lastly, design principles revealed here for the control of photophysical and electron-transfer processes will be useful for constructing new MOF-derived visible- and infrared-based optoelectronics.},

  doi          = {10.1021/acs.jpcc.9b10834},

  journal      = {Journal of Physical Chemistry. C},

  number       = 3,

  volume       = 124,

  place        = {United States},

  year         = {Thu Jan 23 00:00:00 EST 2020},

  month        = {Thu Jan 23 00:00:00 EST 2020}

}

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Title: Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C60

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Title: Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C₆₀