Abstract
Sandwich-type (Cs+)2(benzo[18]crown-6)3 and (Cs+)(dibenzo[18]crown-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(benzo[18]crown6)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 benzo[18]crown-6. In the case of Cs +(dibenzo[18]crown-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).
| Original language | English |
|---|---|
| Pages (from-to) | 4454-4461 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 48 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - 2009 May 18 |