Facile Optical Gap Tuning in Nanographene Metal-Organic Frameworks

Xin Zheng; Rosmi Reji; Matthew C. Drummer; Haiying He; Jens Niklas; Nicholas P. Weingartz; Igor L. Bolotin; Lin X. Chen; Oleg G. Poluektov; Peter Zapol; Ksenija D. Glusac

doi:10.1021/acsaom.3c00220

Facile Optical Gap Tuning in Nanographene Metal-Organic Frameworks

Xin Zheng, Rosmi Reji, Matthew C. Drummer, Haiying He, Jens Niklas, Nicholas P. Weingartz, Igor L. Bolotin, Lin X. Chen, Oleg G. Poluektov, Peter Zapol, Ksenija D. Glusac^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

The utilization of metal-organic frameworks (MOFs) in photocatalysis applications requires light-responsive architectures with tunable optical gaps. Here, we demonstrate a facile approach to optical gap tuning via postsynthetic modifications of pbz-MOF-1, a Zr-based MOF with polyphenylene ligands. A simple reaction of pbz-MOF-1 with FeCl₃ was shown to induce three different chemical reactions: oxidative dehydrogenation, chlorination, and one-electron oxidation of the ligands. The result of these reactions was a gradual decrease in the optical gap from 2.95 eV to as little as 0.69 eV. Steady-state and time-resolved optical spectroscopy, mass spectrometry, and electron paramagnetic resonance spectroscopy, coupled with density functional theory calculations, provide insights into the chemical transformations that affect the optical properties of the MOF. The facile optical gap tuning reported here has promising application in the utilization of photoresponsive MOFs in photocatalysis, sensing, and other light-triggered applications.

Original language	English (US)
Pages (from-to)	1643-1650
Number of pages	8
Journal	ACS Applied Optical Materials
Volume	1
Issue number	10
DOIs	https://doi.org/10.1021/acsaom.3c00220
State	Published - Oct 27 2023

Funding

This work is supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences, through Argonne National Laboratory under Contract No. DE-AC02–06CH11357.

Keywords

optical gap tuning
postsynthetic modification
stable aromatic radical cation
transient absorption spectroscopy
zirconium metal-organic frameworks

ASJC Scopus subject areas

Spectroscopy
Electronic, Optical and Magnetic Materials
Atomic and Molecular Physics, and Optics

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10.1021/acsaom.3c00220

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title = "Facile Optical Gap Tuning in Nanographene Metal-Organic Frameworks",

abstract = "The utilization of metal-organic frameworks (MOFs) in photocatalysis applications requires light-responsive architectures with tunable optical gaps. Here, we demonstrate a facile approach to optical gap tuning via postsynthetic modifications of pbz-MOF-1, a Zr-based MOF with polyphenylene ligands. A simple reaction of pbz-MOF-1 with FeCl3 was shown to induce three different chemical reactions: oxidative dehydrogenation, chlorination, and one-electron oxidation of the ligands. The result of these reactions was a gradual decrease in the optical gap from 2.95 eV to as little as 0.69 eV. Steady-state and time-resolved optical spectroscopy, mass spectrometry, and electron paramagnetic resonance spectroscopy, coupled with density functional theory calculations, provide insights into the chemical transformations that affect the optical properties of the MOF. The facile optical gap tuning reported here has promising application in the utilization of photoresponsive MOFs in photocatalysis, sensing, and other light-triggered applications.",

keywords = "optical gap tuning, postsynthetic modification, stable aromatic radical cation, transient absorption spectroscopy, zirconium metal-organic frameworks",

author = "Xin Zheng and Rosmi Reji and Drummer, {Matthew C.} and Haiying He and Jens Niklas and Weingartz, {Nicholas P.} and Bolotin, {Igor L.} and Chen, {Lin X.} and Poluektov, {Oleg G.} and Peter Zapol and Glusac, {Ksenija D.}",

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day = "27",

doi = "10.1021/acsaom.3c00220",

language = "English (US)",

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T1 - Facile Optical Gap Tuning in Nanographene Metal-Organic Frameworks

AU - Zheng, Xin

AU - Reji, Rosmi

AU - Drummer, Matthew C.

AU - He, Haiying

AU - Niklas, Jens

AU - Weingartz, Nicholas P.

AU - Bolotin, Igor L.

AU - Chen, Lin X.

AU - Poluektov, Oleg G.

AU - Zapol, Peter

AU - Glusac, Ksenija D.

PY - 2023/10/27

Y1 - 2023/10/27

N2 - The utilization of metal-organic frameworks (MOFs) in photocatalysis applications requires light-responsive architectures with tunable optical gaps. Here, we demonstrate a facile approach to optical gap tuning via postsynthetic modifications of pbz-MOF-1, a Zr-based MOF with polyphenylene ligands. A simple reaction of pbz-MOF-1 with FeCl3 was shown to induce three different chemical reactions: oxidative dehydrogenation, chlorination, and one-electron oxidation of the ligands. The result of these reactions was a gradual decrease in the optical gap from 2.95 eV to as little as 0.69 eV. Steady-state and time-resolved optical spectroscopy, mass spectrometry, and electron paramagnetic resonance spectroscopy, coupled with density functional theory calculations, provide insights into the chemical transformations that affect the optical properties of the MOF. The facile optical gap tuning reported here has promising application in the utilization of photoresponsive MOFs in photocatalysis, sensing, and other light-triggered applications.

AB - The utilization of metal-organic frameworks (MOFs) in photocatalysis applications requires light-responsive architectures with tunable optical gaps. Here, we demonstrate a facile approach to optical gap tuning via postsynthetic modifications of pbz-MOF-1, a Zr-based MOF with polyphenylene ligands. A simple reaction of pbz-MOF-1 with FeCl3 was shown to induce three different chemical reactions: oxidative dehydrogenation, chlorination, and one-electron oxidation of the ligands. The result of these reactions was a gradual decrease in the optical gap from 2.95 eV to as little as 0.69 eV. Steady-state and time-resolved optical spectroscopy, mass spectrometry, and electron paramagnetic resonance spectroscopy, coupled with density functional theory calculations, provide insights into the chemical transformations that affect the optical properties of the MOF. The facile optical gap tuning reported here has promising application in the utilization of photoresponsive MOFs in photocatalysis, sensing, and other light-triggered applications.

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KW - postsynthetic modification

KW - stable aromatic radical cation

KW - transient absorption spectroscopy

KW - zirconium metal-organic frameworks

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Facile Optical Gap Tuning in Nanographene Metal-Organic Frameworks

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