The dimers [Cu-2(dppm)(2)(CN-t-Bu)(3)](BF4)(2) and [Ag-2(dppm)(2)(CN-t-Bu)(2)](X)(2) (X- = BF4-, CIO4-) and the coordination polymers {[M(diphos)(CN-t-Bu)(2)]BF4}(n) (M = Cu, Ag; diphos = bis(diphenylphosphino) butane (dppb), bis(diphenylphosphino)pentane (dpppen), bis(diphenylphosphino)hexane (dpph)), {[Ag-2(dppb)(3)(CN-t-Bu)(2)](BF4)(2)}(n), and {[Ag(dpppen)(CN-t-Bu)]BF4}(n) have been synthesized and fully characterized as model materials for the mixed bridging ligand polymers which exhibit the general formula {[M(diphos)(dmb)]BF4}(n) (M = Cu, Ag; dmb = 1,8-diisocyano-p-menthane) and {[Ag(dppm)(dmb)]CIO4}(n). The identity of four polymers ({[Ag(dppb)(CN-t-Bu)(x)]BF4}(n) (x = 1, 2), {[Ag-2(dppb)(3)(CN-t-Bu)(2)](BF4)(2)}(n), {[Ag(dppm)(dmb)CIO4}(n)) and the two dimers has been confirmed by X-ray crystallography. The structure of j[Ag(dppm)(dmb)]CIO4}(n), exhibits an unprecedented 1-D chain of the type "{Ag(dmb)(2)Ag(dppm)(2)(2+)}(n)", where d((AgAg)-Ag-...) values between tetrahedral Ag atoms are 4.028(1) and 9.609(1) Angstrom for the dppm and dmb bridged units, respectively. The {[Ag(dppb)(CN-t-Bu)(x)]BF4}(n) polymers (x = 1, 2) form zigzag chains in which the Ag atoms are tri- and tetracoordinated, respectively. The {[Ag-2(dppb)(3)(CN-t-Bu)(2)](BF4)(2)}(n) polymer, which is produced from the rearrangement of {[Ag(dppb)(CN-t-Bu)(2)]BF4}(n), forms a 2-D structure described as a "honeycomb" pattern, where large {Ag(dppb)(+)}(6) macrocycles each hosting two counterions and two acetonitrile guest molecules are observed. Properties such as glass transition temperature, morphology, thermal decomposition, and luminescence in the solid state at 293 K are reported. The luminescence bands exhibit maxima between 475 and 500 nm with emission lifetimes ranging between 6 and 55 mus. These emissions are assigned to a metal-to-ligand charge transfer (MLCT) of the type M(I) --> pi*(NC)/pi*(PPh2).