Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies

Pavel M. Usov; Chanel F. Leong; Bun Chan; Mikihiro Hayashi; Hiroshi Kitagawa; Joshua J. Sutton; Keith C. Gordon; Idan Hod; Omar K. Farha; Joseph T. Hupp; Matthew Addicoat; Agnieszka Beata Kuc; Thomas Heine; Deanna M. D'Alessandro

doi:10.1039/c8cp04157a

Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies

Pavel M. Usov, Chanel F. Leong, Bun Chan, Mikihiro Hayashi, Hiroshi Kitagawa, Joshua J. Sutton, Keith C. Gordon, Idan Hod, Omar K. Farha, Joseph T. Hupp, Matthew Addicoat, Agnieszka Beata Kuc, Thomas Heine, Deanna M. D'Alessandro

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32 Scopus citations

Abstract

The stimuli responsive behaviour of charge transfer donor-acceptor metal-organic frameworks (MOFs) remains an understudied phenomenon which may have applications in tuneable electronic materials. We now report the modification of donor-acceptor charge transfer characteristics in a semiconducting tetrathiafulvalene-naphthalene diimide-based MOF under applied electrochemical bias and pressure. We employ a facile solid state in situ Raman spectroelectrochemical technique, applied for the first time in the characterisation of electroactive MOFs, to monitor the formation of a new complex TTFTC⁺-DPNI from a largely neutral system, upon electrochemical oxidation of the framework. In situ pressure-dependent Raman spectroscopy and powder X-ray diffraction experiments performed in a diamond anvil cell revealed blue shifts in the donor and acceptor vibrational modes in addition to contractions in the unit cell which are indicative of bond shortening. This study demonstrates the utility of in situ Raman spectroscopic techniques in the characterisation of redox-active MOFs and the elucidation of their electronic behaviours.

Original language	English
Pages (from-to)	25772-25779
Number of pages	8
Journal	Physical Chemistry Chemical Physics
Volume	20
Issue number	40
DOIs	https://doi.org/10.1039/c8cp04157a
State	Published - 17 Oct 2018
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2018 the Owner Societies.

Funding

We gratefully acknowledge support from Australian Research Council, SydneyNano and the Vibrational Spectroscopy Core Facility at the University of Sydney. O. K. F. gratefully acknowledges the support of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Science, Basic Energy Sciences Program (Award DE-FG02-17ER16362) J. T. H. acknowledges support from the U.S. Dept. of Energy, Office of Science, Office of Basic Energy Sciences (grant no. DE-FG02-87ER13808). TH acknowledges funding of Deutsche Forschungsgemeinschaft via the priority program COORNETS (SPP 1928, HE 3543/30-1).

Funders	Funder number
Basic Energy Sciences Program	DE-FG02-17ER16362
Office of Basic Energy Sciences
SydneyNano
U.S. DOE
U.S. Dept. of Energy
Office of Science
Australian Research Council	FT170100283
Deutsche Forschungsgemeinschaft	SPP 1928, HE 3543/30-1
University of Sydney

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Usov, P. M., Leong, C. F., Chan, B., Hayashi, M., Kitagawa, H., Sutton, J. J., Gordon, K. C., Hod, I., Farha, O. K., Hupp, J. T., Addicoat, M., Kuc, A. B., Heine, T., & D'Alessandro, D. M. (2018). Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies. Physical Chemistry Chemical Physics, 20(40), 25772-25779. https://doi.org/10.1039/c8cp04157a

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abstract = "The stimuli responsive behaviour of charge transfer donor-acceptor metal-organic frameworks (MOFs) remains an understudied phenomenon which may have applications in tuneable electronic materials. We now report the modification of donor-acceptor charge transfer characteristics in a semiconducting tetrathiafulvalene-naphthalene diimide-based MOF under applied electrochemical bias and pressure. We employ a facile solid state in situ Raman spectroelectrochemical technique, applied for the first time in the characterisation of electroactive MOFs, to monitor the formation of a new complex TTFTC+-DPNI from a largely neutral system, upon electrochemical oxidation of the framework. In situ pressure-dependent Raman spectroscopy and powder X-ray diffraction experiments performed in a diamond anvil cell revealed blue shifts in the donor and acceptor vibrational modes in addition to contractions in the unit cell which are indicative of bond shortening. This study demonstrates the utility of in situ Raman spectroscopic techniques in the characterisation of redox-active MOFs and the elucidation of their electronic behaviours.",

author = "Usov, {Pavel M.} and Leong, {Chanel F.} and Bun Chan and Mikihiro Hayashi and Hiroshi Kitagawa and Sutton, {Joshua J.} and Gordon, {Keith C.} and Idan Hod and Farha, {Omar K.} and Hupp, {Joseph T.} and Matthew Addicoat and Kuc, {Agnieszka Beata} and Thomas Heine and D'Alessandro, {Deanna M.}",

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doi = "10.1039/c8cp04157a",

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Usov, PM, Leong, CF, Chan, B, Hayashi, M, Kitagawa, H, Sutton, JJ, Gordon, KC, Hod, I, Farha, OK, Hupp, JT, Addicoat, M, Kuc, AB, Heine, T & D'Alessandro, DM 2018, 'Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies', Physical Chemistry Chemical Physics, vol. 20, no. 40, pp. 25772-25779. https://doi.org/10.1039/c8cp04157a

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AU - Hayashi, Mikihiro

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AU - Sutton, Joshua J.

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AU - Hod, Idan

AU - Farha, Omar K.

AU - Hupp, Joseph T.

AU - Addicoat, Matthew

AU - Kuc, Agnieszka Beata

AU - Heine, Thomas

AU - D'Alessandro, Deanna M.

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AB - The stimuli responsive behaviour of charge transfer donor-acceptor metal-organic frameworks (MOFs) remains an understudied phenomenon which may have applications in tuneable electronic materials. We now report the modification of donor-acceptor charge transfer characteristics in a semiconducting tetrathiafulvalene-naphthalene diimide-based MOF under applied electrochemical bias and pressure. We employ a facile solid state in situ Raman spectroelectrochemical technique, applied for the first time in the characterisation of electroactive MOFs, to monitor the formation of a new complex TTFTC+-DPNI from a largely neutral system, upon electrochemical oxidation of the framework. In situ pressure-dependent Raman spectroscopy and powder X-ray diffraction experiments performed in a diamond anvil cell revealed blue shifts in the donor and acceptor vibrational modes in addition to contractions in the unit cell which are indicative of bond shortening. This study demonstrates the utility of in situ Raman spectroscopic techniques in the characterisation of redox-active MOFs and the elucidation of their electronic behaviours.

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Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies

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