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| - The Big Squeeze: Guest Exchange in an M4L6Supramolecular Host
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| Abstract
| - Guest exchange in an M4L6 supramolecular host has been evaluated to determine whether hostrupture is required for guest ingress and egress. Two mechanistic models were evaluated: one requiringpartial dissociation of the host structure to create a portal for guest passage and one necessitatingdeformation of the host structure to create a dilated aperture for guest passage without host rupture. Threerelated lines of inquiry support the nondissociative guest exchange mechanism. (a) Equally facile guestexchange is observed in labile ([Ga4L6]12-) and inert ([Ti4L6]8- and [Ge4L6]8-) hosts. (b) Molecular mechanicscalculations demonstrate that the structural deformations required for enlargement of an M4L6 aperture ina nonrupture or nondissociative guest exchange mechanism are plausible. (c) As predicted by thecalculations, CoCp*2+, a sterically demanding guest, significantly inhibits guest exchange. These resultsbring new insight to the application of the M4L6 supramolecular host for encapsulated reaction chemistryfor which there are now several examples.
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