Crystalline Supramolecular Gyroscope with a Water Molecule as an Ultrasmall Polar Rotator Modulated by Charge-Assisted Hydrogen Bonds.

A new strategy for the construction of crystalline molecular rotors is presented. The combination of a conformation-modifiable macrocyclic host and two cooperative guests affords one supramolecular gyroscope-like compound, (t-BuNH3)(18-crown-6)[ZnCl3(H2O)], in which the coordinated water molecule functions as an ultrasmall polar rotator, revealed by its significant dielectric relaxation and the molecular dynamics simulations. In addition, such a compound can reversibly undergo a polar-to-polar phase transition triggered by the changed conformation of the 18-crown-6 host, leading to a switchable on/off rotation of water molecule, well controlled by strength and direction of charge-assisted hydrogen bonds.

A near-room-temperature organic-inorganic hybrid ferroelectric: [C6H5CH2CH2NH3]2[CdI4].

An organic-inorganic hybrid compound, [C6H5CH2CH2NH3]2[CdI4], exhibits a reversible ferroelectric phase transition at 301/297 K. Switchable dielectric constant, second harmonic generation, and pyroelectricity were synchronously observed accompanied by the order-disorder phase transition. This finding promotes research on molecular ferroelectrics to search for promising multifunctional switching materials at near room temperature.

Molecular Dynamics of Flexible Polar Cations in a Variable Confined Space: Toward Exceptional Two-Step Nonlinear Optical Switches.

The changeable molecular dynamics of flexible polar cations in the variable confined space between inorganic chains brings about a new type of two-step nonlinear optical (NLO) switch with genuine "off-on-off" second harmonic generation (SHG) conversion between one NLO-active state and two NLO-inactive states.