Mononuclear [Zn(FcCOO)(DTBbpy)2]ClO4.(H2O)3 (1) and dinuclear [Cd2(FcCOO)2(DTBbpy)4]ClO4·(H2O) (2), [Pb2(FcCOO)2(DTBbpy)2(H2O)2]·ClO4 (3) (FcCOO = ferrocenecarboxylate, DTBbpy = 4,4′-di-tert-butyl-bipyridyl) metal complexes have been synthesized and characterized by single crystal X-ray diffraction. It reveals that the Zn(II), Cd(II) and Pb(II) metal complexes have different coordination geometries [Zn and Pb = distorted octahedral, Cd = distorted pentagonal bipyramidal]. The compound 3 shows the hemidirected mode of coordination in the geometrical system due to the inert pair effect of the lone pair of an electron on Pb(II) metal atom. The molecules are further forms 2D & 3D framework structure via intermolecular hydrogen bonding. All the three compounds exhibit strong fluorescence emission bands in the liquid state at ambient temperature, of which the emission maxima show red-shifted and the solution-state electrochemistry of compounds 1–3 in CH3CN has been investigated.