The molecular building blocks Fe(II)Pc (Pc = phthalocyaninato(2-)), Fe(III)Pc, ZnPc, Cp(dppe)Fe, and Cp(PPh3)(2)Ru were combined in the cyanide-bridged dinuclear reference compounds with M-CN-ZnPc and M-CN-FePc-CN arrays containing Fe(LI)Pc and Fe(III)Pc. The linear trinuclear species with the M(mu-CN)Fe(mu-CN)M' backbone were prepared for both Fe(II)Pc and Fe(III)Pe centers, for terminal Fe/Fe, Fe/Ru, and Ru/Ru combinations and for all three possible cyanide orientations (M-CN-Fe-NC-M', M-CN-Fe-CN-M', and M-NC-Fe-CN-M'). The 15 complexes obtained were identified from their IR spectra and six structure determinations. The preferred orientation of the cyanide bridges could be established starting from the [Fe-NC-Fe(III)Pc-CN-Fe](+) complex, which is labile in solution and isomerizes to the corresponding [Fe-CN-Fe(III)Pc-NC-Fe](+) complex. A kinetic analysis of this isomerization has yielded an activation barrier of roughly 110 kJ/mol.