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

Chem Sci. 2017 Aug 1;8(8):5356-5361. doi: 10.1039/c7sc01041a. Epub 2017 Jun 19.

Authors

Ming Zhang¹, Tao Yang^{2

1}, Zhenxing Wang³, Xiong-Feng Ma¹, Yuexing Zhang², Samuel M Greer^{4

5}, Sebastian A Stoian^{4

5}, Zhong-Wen Ouyang³, Hiroyuki Nojiri⁶, Mohamedally Kurmoo⁷, Ming-Hua Zeng^{2

1}

Affiliations

¹ Department of Chemistry and Pharmaceutical Sciences , Guangxi Normal University , Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources , Guilin , 541004 , P. R. China.
² College of Chemistry and Chemical Engineering , Hubei University , Wuhan , 430062 , P. R. China . Email: zmh@hubu.edu.cn.
³ Wuhan National High Magnetic Field Center & School of Physics , Huazhong University of Science and Technology , Wuhan , 430074 , P. R. China.
⁴ Department of Chemistry and Biochemistry , Florida State University , Tallahassee , Florida 32306 , USA.
⁵ National High Magnetic Field Laboratory , Florida State University , Tallahassee , Florida 32310 , USA.
⁶ Institute for Materials Research , Tohoku University , Katahira 2-1-1 , Sendai 980-8577 , Japan.
⁷ Institut de Chimie de Strasbourg , CNRS-UMR 7177 , Université de Strasbourg , 4 rue Blaise Pascal , 67070 Strasbourg , France . Email: 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 FeII4(mbm)₄Cl₄(MeOH)₄ were exposed to air to give black [FeIII4(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.