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

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

Ming Zhang  1 , Tao Yang  2   1 , Zhenxing Wang  3 , Xiong-Feng Ma  1 , Yuexing Zhang  2 , Samuel M Greer  4   5 , Sebastian A Stoian  4   5 , Zhong-Wen Ouyang  3 , Hiroyuki Nojiri  6 , Mohamedally Kurmoo  7 , Ming-Hua Zeng  2   1
Affiliations

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

Ming Zhang et al. Chem Sci. .

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.

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Figures

Fig. 1
Fig. 1. Reaction leading to FeII4(mbm)4Cl4(MeOH)4 and its transformation into [FeIII4(mbm)4Cl4(OH)4]·2H2O. Top: the syntheses adopted. Bottom: time-dependent microscopy photographs of the crystals that were post-synthetically transformed during exposure to air (27 °C, 56% RH).
Fig. 2
Fig. 2. Details of the crystal structures of 1 (left, a and b) and 1-2d (right, c and d). Top: the coordination modes of Fe; bottom: discrete clusters viewed along the c-axis showing the different orientations of the Cl atoms.
Fig. 3
Fig. 3. Single crystal X-ray diffraction as a function of exposure time. (a) The diffraction frames and (b) 3D shapes of selected Bragg reflections for 1 after exposure to air for 0 h (left), 24 h (middle) and 48 h (right).
Fig. 4
Fig. 4. (a) The temperature dependence of χ g T in 1 kOe for the samples that were exposed to air for different periods of time. The solid lines represent the theoretical fits using the parameters given in the ESI; (b) their isothermal magnetisation at 2 K; and (c) zero-field 57Fe Mössbauer spectra at 80 K for the fresh sample (1), and samples of 1-8h, 1-15h, 1-2d, and 1-180d that were exposed to air. The simulations shown in red correspond to the sum of all of the components.
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