Encapsulated water in a supramolecular $Ga_4$L_6$^{-12}$ cage is neither ice- nor bulk water-like

Sebastiani Federico, Bender Trandon A., Pezzotti Simone, Li Wan-Lu,Schwaab Gerhard,Bergman Robert G.大牛学者,Raymond Kenneth N.大牛学者,Toste F. Dean大牛学者,Head-Gordon Teresa,Havenith Martina


引用 0|浏览14
Using THz absorption spectroscopy and ab initio molecular dynamics, we have investigated the water confined in a $Ga_4$L_6$^{-12}$ supramolecular tetrahedral assembly under ambient conditions. Based on the difference between the THz spectra of $Ga_4$L_6$^{-12}$ and a water-filled cavity compared to the nanocapsule occupied with a tetraethylammonium cation ($Et_4$N$^{+}$), we have experimentally determined that a small dynamically distinct network of 9$\pm$1 water molecules is present within the cavity of the $Ga_4$L_6$^{-12}$ supramolecular host. The low-frequency spectroscopic fingerprints and theoretical results of the water in the $Ga_4$L_6$^{-12}$ host assembly demonstrate that the structure of encapsulated water is different from that of ice and bulk water under cold temperatures or higher pressures, characterized by an isolated and arrested water cluster with significant translational and rotational entropy loss. In contrast to previous observations in crystals, the absorption spectrum and theoretical analysis of the encapsulated water under ambient conditions does not resemble a distinct known phase of water. We discuss the entropic implications of the replacement of the confined water by a substrate as part of a whole catalytic cycle for the $Ga_4$L_6$^{-12}$ supramolecular construct.
AI 理解论文