Sandwich-type (Cs+)2(benzocrown-6)3 and (Cs+)(dibenzocrown-6)2 supramolecular cations were introduced as counterions of [Ni(dmit)2]- (dmit2- = 2-thione-1,3-dithiole-4,5-dithiolate) anions to induce unique [Ni(dmit) 2]- anion (S = 1/2) arrangements and magnetic properties. The magnetic exchange energy (J) between the [Ni(dmit)2]- anions was dependent on the mode of the intermolecular interactions. In the case of (Cs+)2(benzocrown6)3[Ni(dmit) 2]-2 (1), the asymmetric arrangement of the [Ni(dmit)2]~ anions involved the coexistence of a w-dimer chain along with a two-dimensional layer via lateral S • • • S contacts, in which the magnetic properties of the π-dimer chain and the two-dimensional layer were characterized by antiferromagnetic (J = -5.2 K) and ferromagnetic coupling (Weiss temperature = +1.1 K), respectively. The unique [Ni(dmit) 2]- arrangements and magnetic behaviors for crystal 1 can be attributed to the asymmetrical benzocrown-6. In the case of Cs +(dibenzocrown-6)2[Ni(dmit)2]- (2), however, the formation of the lateral [Ni(dmit)2]~ dimer via S ⋯ S contacts yielded antiferromagnetic coupling corresponding to the dimer model (J = -25.5 K).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry