Assembly of alternating spin-chains with magnetically anisotropic cobalt(ii) dimers

Abstract

A dimeric carboxylato complex of cobalt(II), [Co₂^II(1,2-chedc)₂(Im)₂] (1) (1,2-chedc = cyclohex-1-ene-1,2-dicarboxylate and Im = imidazole), has been isolated. This complex can be further linked by chloro- or carboxylato-ligands, affording respectively one-dimensional chain structures of ¹_∞[Co₂^II(μ-Cl)₂(1,2-chedc)(Im)₂] (2) and ¹_∞[Co^II(1,2-chedc)(Im)] (3). Compound 1 shows weak antiferromagnetic interactions passing through the body of the dicarboxylate as well as substantial single-ion magnetic anisotropy (zero-field splitting energy Δ = 8.5 cm⁻¹). Both 2 and 3 exhibit typical alternating spin-chain behaviour in the higher-temperature region, but they display disparate behaviours at lower temperatures. For 2, alternating F–AF interactions compete (J₁ = 6.7 K and J₂ = −8.2 K), resulting in paramagnet-like behaviour with no clear evidence of three-dimensional contact. Compound 3 exhibits stronger intrachain AF–AF exchange-coupling interactions (J₁ = −9.3 K and J₂ = −4.3 K), leading to non-diamagnetic ground state due to the tiling of adjacent spins. Long-range magnetic ordering was observed below 10 K. Its narrow hysteresis loop suggests the use of 3 as a soft magnet.