Conformational polymorph of o-aminoanilinium(dibenzo[18]crown-6) supramolecules in [Ni(dmit)2]- salts.

The supramolecular (HOPD(+))(DB[18]crown-6) cation, in which HOPD(+) and DB[18]crown-6 are o-aminoanilinium and dibenzo[18]crown-6, respectively, was introduced into [Ni(dmit)(2)](-) salts (dmit(2-) = 2-thioxo-1,3-dithiole-4,5-dithiolate). Conformational polymorphs were observed as tetragonal (HOPD(+))(DB[18]crown-6)[Ni(dmit)(2)](-) (1) and monoclinic (HOPD(+))(DB[18]crown-6)[Ni(dmit)(2)](-) (2). The ammonium group of HOPD(+) in salts 1 and 2 formed the N-H(+)O hydrogen bonds at the bottom and upper positions of V-shaped DB[18]crown-6, respectively, thereby producing a different supramolecular conformation.

Ferroelectricity and polarity control in solid-state flip-flop supramolecular rotators.

Molecular rotation has attracted much attention with respect to the development of artificial molecular motors, in an attempt to mimic the intelligent and useful functions of biological molecular motors. Random motion of molecular rotators--for example the 180 degree flip-flop motion of a rotatory unit--causes a rotation of the local structure. Here, we show that such motion is controllable using an external electric field and demonstrate how such molecular rotators can be used as polarization rotation units in ferroelectric molecules.

Solid-state molecular rotators of anilinium and adamantylammonium in [Ni(dmit)2](-) salts with diverse magnetic properties.

Supramolecular rotators of hydrogen-bonding assemblies between anilinium (Ph-NH 3 (+)) or adamantylammonium (AD-NH 3 (+)) and dibenzo[18]crown-6 (DB[18]crown-6) or meso-dicyclohexano[18]crown-6 (DCH[18]crown-6) were introduced into [Ni(dmit) 2] salts (dmit (2-) is 2-thioxo-1,3-dithiole-4,5-dithiolate). The ammonium moieties of Ph-NH 3 (+) and AD-NH 3 (+) cations were interacted through N-H (+) approximately O hydrogen bonding with the six oxygen atoms of crown ethers, forming 1:1 supramolecular rotator-stator structures. X-ray crystal-structure analyses revealed a jackknife-shaped conformation of DB[18]crown-6, in which two benzene rings were twisted along the same direction, in (Ph-NH 3 (+))(DB[18]crown-6)[Ni(dmit) 2] (-) ( 1) and (AD-NH 3 (+))(DB[18]crown-6)[Ni(dmit) 2] (-) ( 3), whereas the conformational flexibility of two dicyclohexyl rings was observed in (Ph-NH 3 (+))(DCH[18]crown-6)[Ni(dmit) 2] (-) ( 2) and (AD-NH 3 (+))(DCH[18]crown-6)[Ni(dmit) 2] (-) ( 4).