Chemical reaction within a compact non-porous crystal containing molecular clusters without the loss of crystallinity

Ming Zhang; Tao Yang; Zhenxing Wang; Xiong-Feng Ma; Yuexing Zhang; Samuel M. Greer; Sebastian A. Stoian; Zhong-Wen Ouyang; Hiroyuki Nojiri; Mohamedally Kurmoo; Ming-Hua Zeng

doi:10.1039/C7SC01041A

Chemical reaction within a compact non-porous crystal containing molecular clusters without the loss of crystallinity†

Ming Zhang,‡^b Tao Yang,

‡^ab Zhenxing Wang,‡^c Xiong-Feng Ma,^b Yuexing Zhang,^a Samuel M. Greer,^de Sebastian A. Stoian,

^de Zhong-Wen Ouyang,^c Hiroyuki Nojiri,^f Mohamedally Kurmoo*^g and Ming-Hua Zeng

*^ab

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* Corresponding authors

^a College of Chemistry and Chemical Engineering, Hubei University, Wuhan, P. R. China
E-mail: zmh@hubu.edu.cn

^b Department of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, Guilin, P. R. China

^c Wuhan National High Magnetic Field Center & School of Physics, Huazhong University of Science and Technology, Wuhan, P. R. China

^d Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida, USA

^e National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, USA

^f Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai 980-8577, Japan

^g Institut de Chimie de Strasbourg, CNRS-UMR 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg, France
E-mail: kurmoo@unistra.fr

Abstract

The very rare occurrence of a gas–solid chemical reaction has been found to take place on a molecule within a compact non-porous crystal without destroying its long-range structural order and retaining similar crystal structures when yellow crystals of Fe^II₄(mbm)₄Cl₄(MeOH)₄ were exposed to air to give black [Fe^III₄(mbm)₄Cl₄(OH)₄]·2H₂O. The latter cannot be synthesised directly. The original cluster underwent an exchange of methanol to hydroxide, an oxidation of Fe(II) to Fe(III), a change in stereochemistry and hydration while the packing and space-group remained unaltered.

Chemical Science

Chemical reaction within a compact non-porous crystal containing molecular clusters without the loss of crystallinity†

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Chemical reaction within a compact non-porous crystal containing molecular clusters without the loss of crystallinity

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