Delicate crystal structure changes govern the magnetic properties of 1D coordination polymers based on 3d metal carboxylates

Homo- and heterometallic ID coordination polymers of transition metals (Co-II, Mn-II, Zn-II) have been synthesized by an in-situ ligand generation route. Carboxylato-based complexes [Co(PhCOO)(2)](n) (1a, 1b), [Co(p-MePh-COO)(2)](n) (2), [ZnMn(PhCOO)(4)](n) (3), and [CoZn(PhCOO)(4)](n) (4) (PhCOOH-benzoic acid, p-MePh-COOH=p-methylbenzoic acid) have been characterized by chemical analysis, single-crystal X-ray diffraction, and magnetization measurements. The new complexes 2 and 3 crystallize in orthorhombic space groups Pnab and Pcab respectively. Their crystal structures consist of zigzag chains, with alternating M-II centers in octahedral and tetrahedral positions, which are similar to those of la and 1b. Compound 4 crystallizes in monoclinic space group P2(1)/c and comprises zigzag chains of M-II ions in a tetrahedral coordination environment. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in the heterometallic complexes 3 and 4, while ferromagnetic interactions operate in homometallic compounds (1a, 1b, and 2). Compound 1b orders ferromagnetically at T-C = 3.7 K whereas la does not show any magnetic ordering down to 330 mK and displays typical single-chain magnet (SCM) behavior with slowing down of magnetization relaxation below 0.6 K. Single-crystal measurements reveal that the system is easily magnetized in the chain direction for la whereas the chain direction coincides with the hard magnetic axis in 1b. Despite important similarities, small differences in the molecular and crystal structures of these two compounds lead to this dramatic change in properties.