Supramolecular rotators of (aniliniums)([18]crown-6) in electrically conducting [Ni(dmit)2] crystals.

Supramolecular assemblies of anilinium (Ani(+)) and fluoroanilinium derivatives (FAni(+)) with [18]crown-6 were introduced into electrically conducting [Ni(dmit)(2)] crystals (dmit(2-) is 2-thioxo-1,3-dithiole-4,5-dithiolate). The crystal structures, electrical conductivities, and magnetic susceptibilities of four new crystals of (Ani(+))([18]crown-6)[Ni(dmit)(2)](3) (1), (o-FAni(+))([18]crown-6)[Ni(dmit)(2)](3) (2), (m-FAni(+))([18]crown-6)[Ni(dmit)(2)](3) (3), and (p-FAni(+))([18]crown-6)[Ni(dmit)(2)](3) (4) were examined from the viewpoint of dynamic supramolecular rotator structures within the crystals. The crystal structures, electrical conduction, and magnetic properties were classified into group-I (crystals 1 and 4) and group-II (crystals 2 and 3). The hydrogen-bonding interaction between -NH(3)(+) and the oxygen atoms of [18]crown-6 formed the stand-up configuration of rotator-stator structures of (Ani(+))([18]crown-6) and (FAni(+))([18]crown-6) supramolecules. The potential energy barriers for the 2-fold flip-flop motion of phenyl- and p-fluorophenyl-rings in crystals 1 and 4 had a relatively small magnitude of ∼150 kJ mol(-1), suggesting that rotations of Ani(+) and p-FAni(+) cations around the C-NH(3)(+) axis occurred in the crystals. In contrast, a large magnitude of the potential energy barriers for the rotations of o-FAni(+) and m-FAni(+) cations in crystals 2 and 3 (>600 kJ mol(-1)) resulted in static supramolecular cationic structures. The cation:anion ratio of 1:3 in these crystals yielded a trimer π-stack of [Ni(dmit)(2)] with a semiconductor-like temperature dependence. The magnetic susceptibilities of the static crystals 2 and 3 were reproduced by the one-dimensional antiferromagnetic linear Heisenberg chain through the one-dimensional linear trimer arrangement. The magnetic susceptibilities of dynamic crystals 1 and 4 enhanced electron delocalization through the intratrimer and intertrimer interactions within the trimer stack, where the molecular rotations of Ani(+) and p-FAni(+) cations played an important role.