Two-electron redox-active tricyano iron(ii) complex with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine as a building block for coordination polymers

A new tricyano iron(ii) building unit, [{K(H2O)4}{FeII(CN)3(L)}]·3H2O (1), was synthesized by the reaction of Moor's salts with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (L) as a capping ligand. X-ray structural analysis reveals that the mononuclear iron(ii) tricyano complex consists of one ligand and three cyanide groups, with K+ ions coordinated between neighboring units to form a one-dimensional chain network structure. 1 shows two reversible redox waves at +0.713 and -0.849 V vs. SCE, which are assigned as Fe(ii)/Fe(iii) and L/L˙- processes, respectively. One-dimensional 4,2-ribbon chain type coordination polymers, [MII(H2O)2{FeII(CN)3(L)}2]·6H2O (M = Fe (2) and Mn (3)), were synthesized by using 1 as a building unit. Cryomagnetic studies reveals that 2 and 3 show paramagnetic behaviour of S = 2 and 5/2, respectively. On the other hand, reaction of 1 and Gd(NO3)3·6H2O forms another one-dimensional chain, [GdIII(NO3)2(H2O)3{FeII(CN)3(L)}]·0.5H2O·2CH3OH (4), showing S = 7/2 paramagnetic behaviour.