RESUMEN
Heteroleptic iron complexes with a naphthoquinone-type ligand, 2-(pyridin-2-yl)-1H-naphtho[2,3-d]imidazole-4,9-dione (HL), were synthesized, and their structures and magnetic properties were investigated. Two spin-crossover complexes, [Fe(L)2(L1)] (1, L1 = ethylenediamine) and [Fe(L)2(L2)] (2, L2 = cyclohexanediamine) were structurally characterized at 100 K and 270 K, and their gradual spin crossover behavior observed by magnetic susceptibility measurements and confirmed by Mössbauer spectroscopic analyses. Two homologous iron(ii) complexes, [Fe(L)2(L3c)] (3, L3c = diimino benzoquinone) and [Fe(L)2(L4c)] (4, L4c = iminosuccinonitrile), were found to exist in the low-spin state in the range of 10-300 K. In contrast, the corresponding complex with two water ligands, [Fe(L)2(H2O)2] (5), and the tris-chelate complex with protonated ligands (HL), [Fe(HL)3](BF4)2 (6), were found to be high-spin.
RESUMEN
Three anthraquinone-type multidentate ligands, HL1-3 (HL = 2-R-1H-anthra[1,2-d]imidazole-6,11-dione; HL1: R = (2-pyridyl), HL2; R = (4,6-dimethyl-2-pyridyl), HL3; R = (6-methoxy-2-pyridyl)), were prepared, and their complexation behaviour was investigated. Three bis-chelate cobalt complexes with the formula [CoII(L1-3)2]·n(solv.) (1, 2, and 3 for HL1, HL2, and HL3, respectively), in which the ligands adopted tridentate binding modes, were synthesized and structurally characterized by single-crystal X-ray analyses. Electrochemical studies of 1-3 in CH2Cl2 reveal three reversible redox waves, assigned to ligand and cobalt-centred processes. Additional complexes were obtained in which HL1 adopted a bidentate binding mode, stabilising the mono-chelate [CoII(HL1)(NO3)2(DMF)2] (4) species and tris-chelate [CoIII(L1)3] (5) complex in which the cobalt ion was in its 3+ state. The electrochemical properties of complex 5 were investigated in DMF, and the Co(ii)/Co(iii) redox couple was found to be negatively shifted compared to that of complex 1, while the ligand-based processes became irreversible. Tridentate chelation is found to stabilise the anthraquinone ligands and unlocks their redox multi-stability.
