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,^a Chanel F. Leong,^a Bun Chan,

^ab Mikihiro Hayashi,^c Hiroshi Kitagawa,

^c Joshua J. Sutton,^d Keith C. Gordon,

^d Idan Hod,^e Omar K. Farha,^e Joseph T. Hupp,^e Matthew Addicoat,^fg Agnieszka Beata Kuc,^gh Thomas Heine

^ghi and Deanna M. D’Alessandro

*^a

Author affiliations

* Corresponding authors

^a School of Chemistry, The University of Sydney, New South Wales 2006, Australia
E-mail: deanna.dalessandro@sydney.edu.au

^b Graduate School of Engineering, Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan

^c Division of Chemistry, Graduate School of Science, Kyoto University 606-8501, Japan

^d Department of Chemistry, University of Otago, Dunedin 9016, New Zealand

^e Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, USA

^f School of Science and Technology, Nottingham Trent University, UK

^g Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Universität Leipzig, Germany

^h Helmholtz Center Dresden-Rossendorf, Institute of Resource Ecology, Leipzig Branch, Permoserstr. 15, D-04318 Leipzig, Germany

ⁱ School of Science, Faculty of Chemistry and Food Chemistry, TU Dresden, Mommsenstr. 13, 01062 Dresden, Germany

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.

Physical Chemistry Chemical Physics

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

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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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