A series of new organometallic polymers of the type {[M(dmb)(2)]Y}(n) (dmb = 1,8-diisocyano-p-menthane; Y = BF4-, NO3-, ClO4-, M = Cu; Y = BF4-, PF4-, NO3-, CH3CO2-, ClO4-; M = Ag) are reported. These materials have been characterized from single-crystal X-ray diffraction (for {[Ag(dmb)(2)]Y}(n); Y = BF4-, NO3-, ClO4-), X-ray powder diffraction (which established the isostructurality between M = Cu and Ag and the relative crystallinity level), differential scanning calorimetry (DSC), solid-state magic spinning angle and solution C-13-NMR, and spin-lattice relaxation time measurements (T-1, C-13-NMR). Three synthesis methods were employed in order to obtain highly crystalline, semicrystalline, and highly amorphous {[Cu(dmb)(2)]BF4}(n) polymers. One polymer has been successfully characterized from a light-scattering technique. For the amorphous {[Cu(dmb)(2)]BF4}(n) polymer, the molecular weights averaged 160 000. The Ag polymers are found to be rather crystalline and exhibit very low solubility properties. Except for the {[Ag(dmb)(2)]PF6}(n) and the highly crystalline {[Cu(dmb)(2)]BF4}(n) materials, all polymers exhibit glass transitions in the 37-96 degrees C (305-340 K) range, even if the materials exhibit a very large crystallinity level. The {[M(dmb)(2)]Y}(n) organometallic materials (M = Cu, Ag; Y = BF4-, PF6-, NO3-, CH3CO2-) are also strongly luminescent in the visible range (400-600 nm) at 77 K, exhibiting polyexponential emission decay traces (either in the solid state or in solutions). By comparison with the emission properties of the non-polymeric [M(CN-t-Bu)(4)](BF4) compounds (M = Cu, Ag) as a model for a monomeric unit, the first and shea-lived component of the emission decay traces (30-90% in relative intensity) is associated with a higher-energy emission localized at one M center within the polymer ("monomer-like emission"). This is also confirmed by time-resolved emission spectroscopy from the comparision with the emission maxima. The other components in the polyexponential decays are associated with lower-energy emissions that are only present in the polymers. This phenomenon is associated with an energy transfer metal-to-metal delocalized along the M chain somewhat similar to the exciton phenomenon known in organic solids.The depolarization of the emission Light confirms the phenomenon. From density functional theory calculations, the lowest energy excited states have been assigned as MLCT (metal-to-ligand charge transfer) with the HOMO being the M centered d orbitals, and the LUMO being the pi* MO centered on the isocyanide groups. X-ray data for {[Ag(dmb)(2)]BF4}(n): space group P2(1)2(1)2(1), orthorhombic, a 9.3273(18) Angstrom, b = 13.685(2) Angstrom, c = 22.124(4) Angstrom, V = 2824.0(9) Angstrom(3), Z = 4, D-calc = 1.353 g/cm(3), R = 0.068, R(w) = 0.073. {[Ag(dmb)(2)]-NO3 . 0.70H(2)O}(n): space group P2(1) /c, monoclinic, a = 13.1746(14) Angstrom, b = 9.7475(11) Angstrom, c = 23.207(3) A, beta = 105.15(1)degrees, V = 2876. 5(6) Angstrom(3), Z = 4, D-calc = 1.297 g/cm(3), R = 0.051, R(w) = 0.048. {[Ag(dmb)(2)]ClO4}(n): space group P2(1)2(1)2(1), orthorhombic, a 9.282(2) Angstrom, b = 13.772(2) Angstrom, c = 22.091(3) Angstrom, V = 2824.1(9) Angstrom(3), Z = 4, D-calc = 1.282 g/cm(3), R = 0.034, R(w) = 0.077.