Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide: a structural, spectroscopic and computational study

Chanel F. Leong; Bun Chan; Tianfu Liu; Harrison S. Moore; Idan Hod; Marcello B. Solomon; Pavel M. Usov; Joseph T. Hupp; Omar Farha; Deanna M. D’Alessandro

doi:10.1039/d2nj00643j

Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide: a structural, spectroscopic and computational study

Chanel F. Leong, Bun Chan, Tianfu Liu, Harrison S. Moore, Idan Hod, Marcello B. Solomon, Pavel M. Usov, Joseph T. Hupp, Omar Farha, Deanna M. D’Alessandro

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

2 Scopus citations

Abstract

Tetrathiafulvalene (TTF) is a highly tunable electron donor that has been widely studied in charge transfer (CT) complexes, including Bechgaard salts which are superconductors at low temperatures. Its close relative, tetrathianaphthalene (TTN) has received considerably less attention than its TTF counterpart but is potentially a versatile electron donor. Three novel CT complexes containing mixed and segregated stack donor-acceptor (D-A) complexes of tetrathiafulvalene (TTF), tetrathianaphthalene (TTN) and naphthalene diimide (NDI) are reported. We demonstrate a facile mechanochemical synthesis of two salts, TTF-DPNI and TTN-DPNI (DPNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide), which is uncommon for these materials. Despite the detection of a very low partial charge transfer in the three salts using UV-Vis-NIR, Raman and EPR spectroscopies, we elucidated the properties of the TTN core with support from DFT calculations for the first time. We highlight the performance of TTN in a CT complex and demonstrate the importance of a combined approach to the characterisation of CT in organic D-A complexes.

Original language	English
Pages (from-to)	10026-10036
Number of pages	11
Journal	New Journal of Chemistry
Volume	46
Issue number	21
DOIs	https://doi.org/10.1039/d2nj00643j
State	Published - 25 Apr 2022
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2022 The Royal Society of Chemistry

Funding

We gratefully acknowledge support from the Australian Research Council (ARC) and the Sydney Analytical Core Research Facility at the University of Sydney. B. C. acknowledges the support of the Japan Society for the Promotion of Science and the provision of computational resources from RIKEN Office for Information Systems and Cybersecurity. O. K. F. acknowledges the support of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Science, Basic Energy Sciences Program (grant no. 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).

Funders	Funder number
U.S. Department of Energy
Basic Energy Sciences Program	DE-FG02-17ER16362
Australian Research Council
RIKEN
University of Sydney
Basic Energy Sciences	DE-FG02-87ER13808
Japan Society for the Promotion of Science
Office of Science
U.S. Department of Energy

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Leong, C. F., Chan, B., Liu, T., Moore, H. S., Hod, I., Solomon, M. B., Usov, P. M., Hupp, J. T., Farha, O., & D’Alessandro, D. M. (2022). Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide: a structural, spectroscopic and computational study. New Journal of Chemistry, 46(21), 10026-10036. https://doi.org/10.1039/d2nj00643j

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title = "Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide: a structural, spectroscopic and computational study",

abstract = "Tetrathiafulvalene (TTF) is a highly tunable electron donor that has been widely studied in charge transfer (CT) complexes, including Bechgaard salts which are superconductors at low temperatures. Its close relative, tetrathianaphthalene (TTN) has received considerably less attention than its TTF counterpart but is potentially a versatile electron donor. Three novel CT complexes containing mixed and segregated stack donor-acceptor (D-A) complexes of tetrathiafulvalene (TTF), tetrathianaphthalene (TTN) and naphthalene diimide (NDI) are reported. We demonstrate a facile mechanochemical synthesis of two salts, TTF-DPNI and TTN-DPNI (DPNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide), which is uncommon for these materials. Despite the detection of a very low partial charge transfer in the three salts using UV-Vis-NIR, Raman and EPR spectroscopies, we elucidated the properties of the TTN core with support from DFT calculations for the first time. We highlight the performance of TTN in a CT complex and demonstrate the importance of a combined approach to the characterisation of CT in organic D-A complexes.",

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day = "25",

doi = "10.1039/d2nj00643j",

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Leong, CF, Chan, B, Liu, T, Moore, HS, Hod, I, Solomon, MB, Usov, PM, Hupp, JT, Farha, O & D’Alessandro, DM 2022, 'Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide: a structural, spectroscopic and computational study', New Journal of Chemistry, vol. 46, no. 21, pp. 10026-10036. https://doi.org/10.1039/d2nj00643j

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T1 - Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide

T2 - a structural, spectroscopic and computational study

AU - Leong, Chanel F.

AU - Chan, Bun

AU - Liu, Tianfu

AU - Moore, Harrison S.

AU - Hod, Idan

AU - Solomon, Marcello B.

AU - Usov, Pavel M.

AU - Hupp, Joseph T.

AU - Farha, Omar

AU - D’Alessandro, Deanna M.

PY - 2022/4/25

Y1 - 2022/4/25

N2 - Tetrathiafulvalene (TTF) is a highly tunable electron donor that has been widely studied in charge transfer (CT) complexes, including Bechgaard salts which are superconductors at low temperatures. Its close relative, tetrathianaphthalene (TTN) has received considerably less attention than its TTF counterpart but is potentially a versatile electron donor. Three novel CT complexes containing mixed and segregated stack donor-acceptor (D-A) complexes of tetrathiafulvalene (TTF), tetrathianaphthalene (TTN) and naphthalene diimide (NDI) are reported. We demonstrate a facile mechanochemical synthesis of two salts, TTF-DPNI and TTN-DPNI (DPNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide), which is uncommon for these materials. Despite the detection of a very low partial charge transfer in the three salts using UV-Vis-NIR, Raman and EPR spectroscopies, we elucidated the properties of the TTN core with support from DFT calculations for the first time. We highlight the performance of TTN in a CT complex and demonstrate the importance of a combined approach to the characterisation of CT in organic D-A complexes.

AB - Tetrathiafulvalene (TTF) is a highly tunable electron donor that has been widely studied in charge transfer (CT) complexes, including Bechgaard salts which are superconductors at low temperatures. Its close relative, tetrathianaphthalene (TTN) has received considerably less attention than its TTF counterpart but is potentially a versatile electron donor. Three novel CT complexes containing mixed and segregated stack donor-acceptor (D-A) complexes of tetrathiafulvalene (TTF), tetrathianaphthalene (TTN) and naphthalene diimide (NDI) are reported. We demonstrate a facile mechanochemical synthesis of two salts, TTF-DPNI and TTN-DPNI (DPNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide), which is uncommon for these materials. Despite the detection of a very low partial charge transfer in the three salts using UV-Vis-NIR, Raman and EPR spectroscopies, we elucidated the properties of the TTN core with support from DFT calculations for the first time. We highlight the performance of TTN in a CT complex and demonstrate the importance of a combined approach to the characterisation of CT in organic D-A complexes.

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Charge transfer in mixed and segregated stacks of tetrathiafulvalene, tetrathianaphthalene and naphthalene diimide: a structural, spectroscopic and computational study

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