On the nature of the transition state characterizing gated molecular encapsulations.

Xiaoyong Lu, Bao-Yu Wang, Shigui Chen, Jovica D Badjić

Index: Molecules 19(9) , 14292-303, (2014)

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Abstract

Gated molecular encapsulations, with baskets of type 1, are postulated to occur by the mechanism in which solvent molecule penetrates the inner space of 1, through one of its apertures, while the residing guest simultaneously departs the cavity. In the transition state of the exchange, three pyridine-based gates are proposed to assume an open position with both incoming solvent and departing guest molecules interacting with the concave surface of the host. The More O'Ferrall-Jencks diagram and linear free energy relationships (LFERs) suggest a more advanced departure of the guest when bigger solvents partake in the displacement.