Supramolecular cation assemblies of hydrogen-bonded (NH4+/NH2NH3+)(crown ether) in [Ni(dmit)2]-based molecular conductors and magnets.

摘要: Hydrogen-bonded supramolecular cation assemblies of (NH4+/NH2−NH3+)(crown ether), where the crown ether is [12]crown-4, [15]crown-5, or [18]crown-6, were incorporated into electrically conducting [Ni(dmit)2] salts (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate). (NH4+)([12]crown-4)[Ni(dmit)2]3(CH3CN)2 had a pyramidal shape, while ionic channels observed in (NH4+)0.88([15]crown-5)[Ni(dmit)2]2 and (NH4+)0.70([18]crown-6)[Ni(dmit)2]2. Both (NH4+)0.88([15]crown-5) (NH4+)0.70([18]crown-6) contained regularly spaced stacks formed by N−H···O hydrogen bonding between oxygen atoms ethers NH4+ ion. occurred nonstoichiometrically; there vacant sites channels. The radius larger than cavity [15]crown-5 [18]crown-6. Therefore, ions could not pass through distributed randomly static disorder caused conduction electrons to be localized [Ni(dmit)2...