Abstract
The inclusion chemistry of the title complex was revisited in the context of three topical problems of present-day crystal engineering: conventional and pseudo-polymorphism, the design of organic zeolite mimics, and the creation of “third generation” porous metal−organic frameworks. The crystal structures of dense (α) and microporous (β) polymorphs of the complex were redetermined and two new crystal structures were studied: β- and γ-inclusion phases of the complex (1:1 and 1:2 host-to-guest ratio, respectively) with benzene as the simplest aromatic guest. Although both the β- and γ-crystal architectures display a remarkable adaptability toward inclusion of various guests, the mechanisms of this adaptability are essentially different. The microporous β-phase is capable of expanding by 14.5% in response to the size of the included guest or variations in temperature. This flexibility is the highest ever observed for a metal−organic microporous framework and is responsible for the zeolitic behavior of the material. In contrast, the γ-phase shows an ability to transform to a number of architectures that are topologically similar but crystallographically different.
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