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Iodine adsorption in a redox-active metal–organic framework: electrical conductivity induced by host−guest charge-transfer

DOI: 10.1021/acs.inorgchem.9b02176 DOI Help

Authors: Xinran Zhang (University of Manchester) , Ivan Da Silva (ISIS Facility) , Rodrigo Fazzi (University of Manchester; Universidade de Sao Paulo) , Alena M. Sheveleva (University of Manchester; Siberian Branch of the Russian Academy of Sciences and Novosibirsk State University) , Xue Han (University of Manchester) , Ben F. Spencer (University of Manchester) , Sergey A. Sapchenko (University of Manchester; Nikolaev Institute of Inorganic Chemistry; Novosibirsk State University) , Floriana Tuna (University of Manchester) , Eric J. L. Mcinnes (University of Manchester) , Ming Li (University of Nottingham) , Sihai Yang (University of Manchester) , Martin Schroder (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Inorganic Chemistry

State: Published (Approved)
Published: September 2019
Diamond Proposal Number(s): 21079

Open Access Open Access

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.

Subject Areas: Chemistry, Materials


Instruments: I11-High Resolution Powder Diffraction

Added On: 07/10/2019 10:58

Documents:
yrrh444.pdf

Discipline Tags:

Radioactive Materials Physical Chemistry Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction