Porous crystals formed from macrocycles with a well-defined cavity potentially provide a specific space for molecular recognition and reactions on the inner surfaces. We have previously reported a single-crystalline metal–macrocycle framework (MMF), formed from trinuclear PdII macrocyclic complexes, with a nano-channel pore for molecular adsorption [1]. The inner surface possesses five types of enantio-paired molecular binding sites per a unit structure. This structural feature enables site- and orientation-selective binding of a wide variety of aromatic molecules with a functional group. In most cases, the guest inclusion takes place reversibly in a crystal-to-crystal manner, and therefore the position and orientation of adsorbed guest molecules can be determined exactly by single-crystal X-ray diffraction at the atomic resolution. Herein we report co-encapsulation of multiple different molecules for expanding their usability and designability. For instance, three different guest molecules, TTF, ferrocene, and fluorene, were site-selectively arranged on the pore surfaces of MMF. The position and orientation of the adsorbed molecules were unambiguously determined by single-crystal X-ray diffraction analysis [2]. Moreover, in situ X-ray snapshot analysis of the guest inclusion successfully found a transient state of multi-step molecular adsorption prior to equilibrium in a single-crystalline nano-channel of a liquid-filled MMF [3]. This method would allow for the visualization of transient states of a wide range of noncovalent self-assembly processes. X-ray snapshot analysis of some chemical reactions will also be reported. REFERENCES [1] Tashiro, S.; Kubota, R.; Shionoya, M. J. Am. Chem. Soc. 2012, 134, 2461. [2] Tashiro, S.; Umeki, T.; Kubota, R.; Shionoya, M. Angew. Chem. Int. Ed. 2014, 53, 8310. [3] Kubota, R.; Tashiro, S.; Shiro, M.; Shionoya, M. Nat. Chem. 2014, 6, 913.

Supramolecular behaviors in metal-macrocycle frameworks

251st National Meeting (2016)

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