The salts of Zn(II), Cd(ii) and Hg(II) react instantaneously with Kpmf (pmf(-) = anion of N,N'-bis(pyrimidine-2-yl)formamidine, Hpmf) in THF, producing bimetallic complexes of the types [M(2)(pmf)(3)](X) (M = Zn(II), X = I(3)(-), ; M = Zn(II), X = NO(3)(-), ; M = Zn(II), X = ClO(4)(-), ; M = Cd(II), X = NO(3)(-), ; M = Cd(II), X = ClO(4)(-), ) and Hg(2)(pmf)(2)X(2) (X = Cl, ; Br, ; I, ). New tridentate and tetradentate coordination modes were observed for the pmf(-) ligands and their fluxional behaviors investigated by measuring variable-temperature (1)H NMR spectra. Complexes and , which possess only tetradentate coordination modes for the pmf(-) ligands in the solid state show larger free energy of activation (DeltaG(c)( not equal)) for the exchange than complexes and with tetradentate and/or tridentate coordination modes. Complexes and are the first dinuclear Zn(II) and Hg(II) complexes containing formamidinate ligands. Moreover, the separation between the two Hg(II) atoms are 3.4689(9), 3.4933(13) and 3.5320(10) A for complexes , respectively, similar to the sum of van der Waals radii of two Hg(II) atoms which is 3.50(7) A. All the complexes exhibit emissions and the nature of the anions hardly change the emission wavelengths of the complexes with the same metal centers. The emission bands may be tentatively assigned as intraligand (IL) pi-->pi* transitions.