Construction of Self-Assembled Unsymmetrical Nanocapsule Space Ditected to Molecular Devices

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We studied on the construction and elucidation of functions of unsymmetrical molecular capsules self-assembled by hydrogen bonds or metal-coordinations. Our findings in this study are as follows.(1) We synthesized bowl-shaped cavitands 1〜7 with hydrogen-bonding sites or metal-coordination sites. We found that 1 and 3, 4 and 5, and 4, 6, and Pd(dppp)(OTf)_2, self-assemble into hydrogen-bonded heterocapsules 1・3 and 4・5, and metal-coordination heterocapsule 4・6・4[Pd(dppp)]^(8+), respectively.(2) We found that these heterocapsules encapsulate unsymmetrical guests with high orientational selectivity what is called "orientational isomerism".(3) The structural and/or electronic environments of one half-capsule unit of the heterocapsule are different from those of the other half-capsule unit. We found that the delicate balance among electrostatic potential repulsion between the lone pair of the carbonyl oxygen atom of a guest and the aromatic cavity of a cavitand, attractive CH-πinteraction, or attractive CH-halogen (halogen-π) interaction in a heterocapsule-guest assembly influences the orientational isomeric selectivity of unsymmetrical guests within heterocapsule.(4) Fine and/or drastic tuning of capsule space has been attained by alteration of the hydrogen-bonding linker and/or hemispherical cavitand, respectively.