Photoinduced reversible phase transition in a phenothiazine-based metal-organic framework

Zhifeng Xiao; Hannah F. Drake; Gregory S. Day; Jason E. Kuszynski; Hengyu Lin; Haomiao Xie; Peiyu Cai; Matthew R. Ryder; Hong Cai Zhou

doi:10.1016/j.xcrp.2022.101074

Photoinduced reversible phase transition in a phenothiazine-based metal-organic framework

Zhifeng Xiao, Hannah F. Drake, Gregory S. Day, Jason E. Kuszynski, Hengyu Lin, Haomiao Xie, Peiyu Cai, Matthew R. Ryder, Hong Cai Zhou

Neutron & X-Ray Scattering, & Thermophys

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

4 Scopus citations

Abstract

Photoinduced phase transitions in metal-organic frameworks are provoked by structural changes of photoresponsive linkers within the framework under light irradiation. These transitions are rare but fundamentally important as they can bring about light-switchability on a variety of properties of the materials. In this work, phenothiazine as a photoresponsive unit with distinctive photochemical properties is incorporated into a Zn-based metal-organic framework, PCN-401. The structural characterization of PCN-401 revealed a reversible structural transition upon light irradiation. The mechanisms behind the photoinduced phase transition are studied systematically by spectrometric methods and structural stability characterization. Our mechanistic studies successfully showcased how the phenothiazine unit in the framework undergoes structural transformation under light irradiation and how the reversible phase transition leads to the property changes. The findings have emphasized the significance of phenothiazine in photoresponsive materials and can serve as inspiration for the design and understandings of next-generation photoresponsive metal-organic materials.

Original language	English
Article number	101074
Journal	Cell Reports Physical Science
Volume	3
Issue number	10
DOIs	https://doi.org/10.1016/j.xcrp.2022.101074
State	Published - Oct 19 2022

Funding

H.F.D. G.S.D. and M.R.R. acknowledge the US Department of Energy (DOE) Office of Science Graduate Student Research (SCGSR) program for funding. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE under contract no. DE-SC0014664. M.R.R. also acknowledges the US DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division (Separation Sciences) for research funding and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under contract no. DE-AC02-05CH11231 for access to supercomputing resources. This work was produced by UT-Battelle LLC under Contract No. DE-AC05-00OR22725 with the US DOE. H.-C.Z. acknowledges the Robert A. Welch Foundation for a Welch Endowed Chair (A-0030) and the financial support of the Qatar National Research Fund award NPRP9-377-1-080. H.-C.Z. also acknowledges the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the US DOE Office of Science (Basic Energy Sciences) under contract no. DE-SC0001015. In addition, the authors acknowledge the Texas A&M University (TAMU) X-ray Diffraction Laboratory and the NMR User Facility. The facilities of the Materials Characterization Facility (RRID: SCR_022202) at TAMU are acknowledged, and in particular, Dr. Wilson Serem is acknowledged for assistance with the nanoindentation studies. The TAMU Laboratory for Biological Mass Spectrometry (LBMS) facility and Dr. Yohannes Rezenom are gratefully acknowledged. This research used resources at the Advanced Light Source at Lawrence Berkeley National Laboratory (LBNL), a DOE Office of Science User Facility operated under contract no. DE-AC02-05CH11231 by LBNL. Beamline 12.2.1 and Dr. Simon J. Teat (LBNL) are gratefully acknowledged. The manuscript is funded by the Welch Foundation for a Welch Endowed Chair (A-0030), the Qatar National Research Fund (NPRP9-377-1-080), the Oak Ridge Institute for Science and Education (DE-SC0014664), and Basic Energy Sciences (DE-SC0001015). Conceptualization, M.R.R. H.-C.Z. H.F.D. and Z.X.; methodology, H.F.D. and Z.X.; investigation, H.F.D. and Z.X.; materials generation, H.F.D. and H.L.; BET measurements, H.F.D.; spectroscopic measurements, H.F.D. Z.X. and H.L.; EPR data measurement and analyses, H.F.D. J.E.K. and H.X.; theoretical calculations, P.C.; draft writing and editing, Z.X. H.F.D. and G.S.D.; funding acquisition, M.R.R. and H.-C.Z.; all of the authors discussed the data and contributed to the paper. The authors declare no competing interests. H.F.D., G.S.D., and M.R.R. acknowledge the US Department of Energy (DOE) Office of Science Graduate Student Research ( SCGSR ) program for funding. The SCGSR program is administered by the Oak Ridge Institute for Science and Education ( ORISE ) for the DOE under contract no. DE-SC0014664 . M.R.R. also acknowledges the US DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division (Separation Sciences) for research funding and the National Energy Research Scientific Computing Center ( NERSC ), a DOE Office of Science User Facility operated under contract no. DE-AC02-05CH11231 for access to supercomputing resources. This work was produced by UT-Battelle LLC under Contract No. DE-AC05-00OR22725 with the US DOE. H.-C.Z. acknowledges the Robert A. Welch Foundation for a Welch Endowed Chair ( A-0030 ) and the financial support of the Qatar National Research Fund award NPRP9-377-1-080 . H.-C.Z. also acknowledges the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the US DOE Office of Science ( Basic Energy Sciences ) under contract no. DE-SC0001015 . In addition, the authors acknowledge the Texas A&M University (TAMU) X-ray Diffraction Laboratory and the NMR User Facility. The facilities of the Materials Characterization Facility (RRID: SCR_022202) at TAMU are acknowledged, and in particular, Dr. Wilson Serem is acknowledged for assistance with the nanoindentation studies. The TAMU Laboratory for Biological Mass Spectrometry (LBMS) facility and Dr. Yohannes Rezenom are gratefully acknowledged. This research used resources at the Advanced Light Source at Lawrence Berkeley National Laboratory (LBNL), a DOE Office of Science User Facility operated under contract no. DE-AC02-05CH11231 by LBNL. Beamline 12.2.1 and Dr. Simon J. Teat (LBNL) are gratefully acknowledged. The manuscript is funded by the Welch Foundation for a Welch Endowed Chair ( A-0030 ), the Qatar National Research Fund ( NPRP9-377-1-080 ), the Oak Ridge Institute for Science and Education ( DE-SC0014664 ), and Basic Energy Sciences ( DE-SC0001015 ).

Funders	Funder number
LBMS
Office of Science Graduate Student Research
SCGSR
TAMU Laboratory for Biological Mass Spectrometry
U.S. Department of Energy
Welch Foundation	A-0030
Office of Science	DE-AC02-05CH11231
Basic Energy Sciences	DE-SC0001015
Oak Ridge Institute for Science and Education	DE-SC0014664
Lawrence Berkeley National Laboratory
Texas A and M University	SCR_022202
Qatar National Research Fund	NPRP9-377-1-080
Chemical Sciences, Geosciences, and Biosciences Division
UT-Battelle	DE-AC05-00OR22725
National Energy Research Scientific Computing Center

Keywords

light-induced switchable adsorption
metal-organic frameworks
phase transition
phenothiazine
photoresponsive

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10.1016/j.xcrp.2022.101074

Cite this

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title = "Photoinduced reversible phase transition in a phenothiazine-based metal-organic framework",

abstract = "Photoinduced phase transitions in metal-organic frameworks are provoked by structural changes of photoresponsive linkers within the framework under light irradiation. These transitions are rare but fundamentally important as they can bring about light-switchability on a variety of properties of the materials. In this work, phenothiazine as a photoresponsive unit with distinctive photochemical properties is incorporated into a Zn-based metal-organic framework, PCN-401. The structural characterization of PCN-401 revealed a reversible structural transition upon light irradiation. The mechanisms behind the photoinduced phase transition are studied systematically by spectrometric methods and structural stability characterization. Our mechanistic studies successfully showcased how the phenothiazine unit in the framework undergoes structural transformation under light irradiation and how the reversible phase transition leads to the property changes. The findings have emphasized the significance of phenothiazine in photoresponsive materials and can serve as inspiration for the design and understandings of next-generation photoresponsive metal-organic materials.",

keywords = "light-induced switchable adsorption, metal-organic frameworks, phase transition, phenothiazine, photoresponsive",

author = "Zhifeng Xiao and Drake, {Hannah F.} and Day, {Gregory S.} and Kuszynski, {Jason E.} and Hengyu Lin and Haomiao Xie and Peiyu Cai and Ryder, {Matthew R.} and Zhou, {Hong Cai}",

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AU - Xiao, Zhifeng

AU - Drake, Hannah F.

AU - Day, Gregory S.

AU - Kuszynski, Jason E.

AU - Lin, Hengyu

AU - Xie, Haomiao

AU - Cai, Peiyu

AU - Ryder, Matthew R.

AU - Zhou, Hong Cai

PY - 2022/10/19

Y1 - 2022/10/19

N2 - Photoinduced phase transitions in metal-organic frameworks are provoked by structural changes of photoresponsive linkers within the framework under light irradiation. These transitions are rare but fundamentally important as they can bring about light-switchability on a variety of properties of the materials. In this work, phenothiazine as a photoresponsive unit with distinctive photochemical properties is incorporated into a Zn-based metal-organic framework, PCN-401. The structural characterization of PCN-401 revealed a reversible structural transition upon light irradiation. The mechanisms behind the photoinduced phase transition are studied systematically by spectrometric methods and structural stability characterization. Our mechanistic studies successfully showcased how the phenothiazine unit in the framework undergoes structural transformation under light irradiation and how the reversible phase transition leads to the property changes. The findings have emphasized the significance of phenothiazine in photoresponsive materials and can serve as inspiration for the design and understandings of next-generation photoresponsive metal-organic materials.

AB - Photoinduced phase transitions in metal-organic frameworks are provoked by structural changes of photoresponsive linkers within the framework under light irradiation. These transitions are rare but fundamentally important as they can bring about light-switchability on a variety of properties of the materials. In this work, phenothiazine as a photoresponsive unit with distinctive photochemical properties is incorporated into a Zn-based metal-organic framework, PCN-401. The structural characterization of PCN-401 revealed a reversible structural transition upon light irradiation. The mechanisms behind the photoinduced phase transition are studied systematically by spectrometric methods and structural stability characterization. Our mechanistic studies successfully showcased how the phenothiazine unit in the framework undergoes structural transformation under light irradiation and how the reversible phase transition leads to the property changes. The findings have emphasized the significance of phenothiazine in photoresponsive materials and can serve as inspiration for the design and understandings of next-generation photoresponsive metal-organic materials.

KW - light-induced switchable adsorption

KW - metal-organic frameworks

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KW - photoresponsive

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JO - Cell Reports Physical Science

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ER -

Photoinduced reversible phase transition in a phenothiazine-based metal-organic framework

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Keywords

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