Phase Transition and Structure Change of Urea Adducts with n-Paraffins and Paraffin-type Compounds

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Abstract
The phase transition temperatures of urea adducts with many n-paraffins and several paraffin-type compounds were measured by differential thermal analysis and the general structure change causing the phase transitions was revealed by X-ray structure analysis. The ordinary hexagonal adducts (high-temperature form) transform commonly into orthorhombic adducts (low-temperature form) except for a few adducts with guest molecules possessing cylindrical shapes. The phase transition can be regarded as an order-disorder transition with respect to the orientation of the guest molecules about the urea channel axis with a cooperative deformation of the urea channels resulting in the orderly orientation of guest molecules below the transition temperatures. The changes in orientation and motion of the guest molecules through the phase transitions are discussed on the basis of X-ray analysis, potential energy and broad-line NMR.