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

Xinran Zhang | Zendy; Iván da Silva | Zendy; Rodrigo Boni Fazzi | Zendy; Alena M. Sheveleva | Zendy; Xue Han | Zendy; Ben F. Spencer | Zendy; Sergey A. Sapchenko | Zendy; Floriana Tuna | Zendy; Eric J. L. McInnes | Zendy; Ming Li | Zendy; Sihai Yang⧫ | Zendy; Martin Schröder | Zendy

Open Access

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

Author(s) -

Xinran Zhang,

Iván da Silva,

Rodrigo Boni Fazzi,

Alena M. Sheveleva,

Xue Han,

Ben F. Spencer,

Sergey A. Sapchenko,

Floriana Tuna,

Eric J. L. McInnes,

Ming Li,

Sihai Yang⧫,

Martin Schröder

Publication year - 2019

Publication title -

inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.348

H-Index - 233

eISSN - 1520-510X

pISSN - 0020-1669

DOI - 10.1021/acs.inorgchem.9b02176

Subject(s) - chemistry , adsorption , deprotonation , conductivity , redox , electrical resistivity and conductivity , charge (physics) , metal , iodine , metal organic framework , synchrotron , crystallography , chemical physics , inorganic chemistry , organic chemistry , ion , physics , quantum mechanics , nuclear physics , electrical engineering , engineering

We report a comparative study of the binding of I 2 (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(V III ) and its oxidized, deprotonated analogue, MFM-300(V IV ). Adsorption of I 2 in MFM-300(V III ) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the V III centers in the host framework and formation of I 3 - species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δ σ = 7) of I 2 @MFM-300(V III/IV ) in comparison to MFM-300(V III ). In contrast, no host-guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I 2 in MFM-300(V IV ). High-resolution synchrotron X-ray diffraction of I 2 @MFM-300(V III/IV ) confirms the first example of self-aggregation of adsorbed iodine species (I 2 and I 3 - ) into infinite helical chains within a MOF.

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