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Acta Cryst. (2014). A70, C636
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Single-crystal to single-crystal transformations has recently received much attention in the field of crystal engineering. Such transformations not only provide insight into the changes taking place within the crystal at the molecular level, but they also aid our understanding of the structure-property relationships. Discrete crystals have been shown to tolerate considerable dynamic behavior at the molecular level while maintaining their single-crystal character. Examples that are common in the literature include bond formation/cleavage,[1] guest uptake,[2] release or exchange as well as polymorphic phase transformations. However, there are rare examples of the structural transformations on the host framework initiated by removal of guest or change in physical conditions such as temperature or pressure. We have investigated a known doubly-interpenetrated metal organic framework with the formula [Zn2(ndc)2(bpy)] which possesses minimal porosity when activated. We have shown not only that the material converts to its triply-interpenetrated analogue upon desolvation, but that the transformation occurs in a single-crystal to single-crystal manner under ambient conditions.[3] This contribution probes the limits to which a single-crystal material can undergo structural rearrangement while still maintaining the macroscopic integrity of the crystal as a discrete entity.

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Acta Cryst. (2014). A70, C998
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One of the target architectures for porous crystals investigated by our group is the "doughnut-shaped" metallocycle. The "doughnut" shape of the metallocycles prevents them from packing efficiently and results in the formation of crevices, cavities or channels in the packing arrangement. Naturally, owing to close-packing requirements the occurrence of empty space in the crystal structure is energetically unfavourable and therefore the available "space" is usually occupied by solvent molecules. Ideally, the porous phase can be obtained by removing the solvent molecules from the channels without disrupting the host framework. In this regard we have conducted a further investigation of the porous metallocycle previously reported by Barbour et al.[1] Single crystals of a previously reported porous metallocycle [Ag2L2](BF4)2·2CH3CN (1) were grown from acetonitrile and immersed in different organic solvents. The crystals thus treated were subjected to single-crystal X-ray diffraction analysis, which revealed that the acetonitrile guest molecules had been replaced by the solvent that the compound was exposed to, yielding five different solvates: [Ag2L2](BF4)2·2(CH3)2CO (2), [Ag2L2](BF4)2·2CHCl3 (3), [Ag2L2](BF4)2·C6H6 (4), [Ag2L2](BF4)2·C6H4F2 (5), [Ag2L2](BF4)2·C7H8 (6). Thermogravimetric analysis supports these findings.

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Acta Cryst. (2014). A70, C1472
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In order to understand gas sorption processes at the molecular level it is important to correlate physico-chemical data (e.g. sorption isotherms and calorimetric analysis) with structural data. It is therefore desirable to carry out structural elucidation and calorimetric analysis under conditions that closely mimic those of the sorption/desorption experiments. However, the crystallographic analysis of samples under controlled gas environments poses significant technical challenges, particularly given the limited space associated with the sample compartment of standard commercial diffractometer. In this regard, an environmental gas cell has been developed in parallel with a pressure-programmed differential scanning calorimeter. Use of these complementary techniques has provided new insight into features such as pressure-induced phase transformations that give rise to inflections and hysteresis in sorption isotherms. The influence of guest molecules on aspects such as structural flexibility, linear thermal expansion and changes in network interpenetration will be discussed.
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