High pressure supramolecular chemistry is a developing interdisciplinary field. The use of high pressure for the study and fabrication of supramolecular systems has been explored only in the past few years. Such studies would shed light on the nature of the structures and functions of the complex supramolecular architectures. In this review, systematic progress made in this field is introduced based on the recent achievements. Special attention is paid to pressure-driven novel properties and functions of supramolecular assemblies resulting from the changes of molecular conformations, intermolecular interactions and supramolecular arrangements under high pressure.
Kai WangShourui LiXiao TanGuanjun XiaoBingbing LiuBo Zou
Recently, the high pressure study on the TiO_2 nanomaterials has attracted considerable attention due to the typical crystal structure and the fascinating properties of TiO_2 with nanoscale sizes. In this paper, we briefly review the recent progress in the high pressure phase transitions of TiO_2 nanomaterials. We discuss the size effects and morphology effects on the high pressure phase transitions of TiO_2 nanomaterials with different particle sizes, morphologies, and microstructures. Several typical pressure-induced structural phase transitions in TiO_2 nanomaterials are presented, including size-dependent phase transition selectivity in nanoparticles, morphology-tuned phase transition in nanowires, nanosheets,and nanoporous materials, and pressure-induced amorphization（PIA） and polyamorphism in ultrafine nanoparticles and TiO_2-B nanoribbons. Various TiO_2 nanostructural materials with high pressure structures are prepared successfully by high pressure treatment of the corresponding crystal nanomaterials, such as amorphous TiO_2 nanoribbons, α-PbO_2-type TiO_2 nanowires, nanosheets, and nanoporous materials. These studies suggest that the high pressure phase transitions of TiO_2 nanomaterials depend on the nanosize, morphology, interface energy, and microstructure. The diversity of high pressure behaviors of TiO_2 nanomaterials provides a new insight into the properties of nanomaterials, and paves a way for preparing new nanomaterials with novel high pressure structures and properties for various applications.
In situ high pressure XRD diffraction and Raman spectroscopy have been performed on 12 nm CeO2 nanoparticles. Surprisingly, under quasihydrostatic conditions, 12 nm CeO2 nanoparticles maintain the fluorite- type structure in the whole pressure range （0-51 GPa） during the experiments, much more stable than the bulk counterpart （PT-31 GPa）. In contrast, they experienced phase transition at pressure as low as 26 GPa under non- hydrostatic conditions （adopting CsC1 as pressure medium）. Additionally, 32-36 nm CeO2 nanoparticles exhibit an onset pressure of phase transition at 35 GPa under quasihydrostatic conditions, and this onset pressure is much lower than our result. Further analysis shows both the experimental condition （i.e., quasihydrostatic or non-hydrostatic） and grain size effect have a significant impact on the high pressure behaviors of CeO2 nanomaterials.
A systematical study of the orientational behavior of C60 molecules in single wall carbon nanotubes （SWCNTs） with different chirality and diameter has been performed by using a model of an infinite long nanotube filled with two C60 （denoted as C60-1 and C60-2） molecules. We studied the preferred orientation of the C60-1 molecule when the neighboring C60-2 molecule was fixed at the pentagon, double-bond, and hexagon orientations respectively. Our results showed that the C60-1 molecule prefers the pentagon （hexagon） orientation when the tube diameter is smaller （larger） than 1.31nm （1.36nm）. For the tube diameter in between, the preferred molecular orientation of C60-1 changes from pentagon to hexagon with the increasing tube diameter when the neighboring C60-2 molecule is fixed at the pentagon or double-bond orientation. A novel vertex orientation for the C60-1 molecule has been found when the C60-2 molecule is fixed at the hexagon orientation.
