Reactions exchanging the cation in (nBu 4N)[Ni(dmit) 2] to cis-cyclohexane-1,4-diammonium (cis-CHDA) in the presence of crown-6, benzocrown-6 (Bcrown-6) and dibenzocrown-6 (DBcrown-6) yielded crystals of the monovalent [Ni(dmit) 2] complex, namely (cis-CHDA)(crown-6) 2[Ni(dmit) 2] 2 (1), (cis-CHDA)(Bcrown-6) 2[Ni(dmit) 2] 2 (2) and (cis-CHDA)(DBcrown-6) 2[Ni(dmit) 2] 2 (3). The two ammonium groups (-NH 3 +) of the cis-CHDA dication at axial and equatorial positions interact with oxygen atoms of the corresponding upper and lower crown ethers to form sandwich-type supramolecular cationic structures. The lateral [Ni(dmit) 2] - anion arrangements through S-S contacts along the short and long axis of [Ni(dmit) 2] anions were realised in crystals of 1, 2, and 3 by the asymmetrical cis-CHDA dication. The temperature- and frequency-dependent anisotropic dielectric constants of a crystal of 1 were evaluated along the a, b and c axes, where the thermally activated motion of the structurally flexible cis-CHDA dication was consistent with the dielectric responses. The motions, dielectric properties and magnetism of [Ni(dmit) 2] - salts with flexible cis-cyclohexane-1,4-diammonium ion have been investigated.
ASJC Scopus subject areas
- Inorganic Chemistry