X-ray Structure and Magnetic Properties of Heterobimetallic Chains Based on the Use of an Octacyanidodicobalt(III) Complex as Metalloligand

摘要: The assembly of [Co2III(μ-2,5-dpp)(CN)8]2− anions and [MII(CH3OH)2(DMSO)2]2+ cations resulted into the formation two heterobimetallic 1D coordination polymers formula [MII(CH3OH)2(DMSO)2(μ-NC)2Co2III(μ-2,5-dpp)(CN)6]n·4nCH3OH [M = CoII (1)/FeII (2) 2,5-dpp 2,5-bis(2-pyridyl)pyrazine. metalloligand coordinates paramagnetic complex cations, in a bis-monodentate fashion, to give rise neutral chains. Cryomagnetic dc (1.9–300 K) ac (2.0–13 magnetic measurements for 1 2 show presence Co(II)HS (1) Fe(II)HS ions (HS – high-spin), respectively, with D values +53.7(5) −5.1(3) cm−1 slow relaxation 1, this compound being new example SIM transversal anisotropy. Low-temperature Q-band EPR study confirms that value is positive, which reveals occurrence strong asymmetry g-tensors allows rough estimation E/D ratio, whereas silent. Theoretical calculations by CASSCF/NEVPT2 on support results from magnetometry EPR. analysis shows M takes place ground state under external fields through dominant Raman direct spin-phonon processes.