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Iodine Adsorption in a Redox-Active Metal–Organic Framework: Electrical Conductivity Induced by Host−Guest Charge-Transfer

Year: 2019
Type: article
Abstract: We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal–organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3– species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host–guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3–) into infinite helical chains within a MOF.
DOI: 10.1021/acs.inorgchem.9b02176
Authors: Xinran Zhang, Ivan da Silva, Rodrigo Fazzi, Alena M. Sheveleva, Xue Han, Ben F. Spencer, Sergey A. Sapchenko, Floriana Tuna, Eric J. L. McInnes, Ming Li, Sihai Yang, Martin Schröder
Institutions: University of Manchester, Rutherford Appleton Laboratory, Universidade de São Paulo, Novosibirsk State University, Siberian Branch of the Russian Academy of Sciences, International Tomography Center, Nikolaev Institute of Inorganic Chemistry, University of Nottingham
Language: English
Field: Chemistry
Open Access status: hybrid
Estimated APC paid: $5,000
Funders: Royal Society, University of Manchester, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, China Scholarship Council, Engineering and Physical Sciences Research Council, H2020 European Research Council
OpenAlex ID: W2972893189
FWCI: 4.869
Cites: 37
Cited by: 123
Related to: 10