The dimers [Cu(2)(dppm)(2)(CN-t-Bu)(3)](BF(4))(2) and [Ag(2)(dppm)(2)(CN-t-Bu)(2)](X)(2) (X(-) = BF(4)(-), ClO(4)(-)) and the coordination polymers [[M(diphos)(CN-t-Bu)(2)]BF(4)](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)](BF(4))(2)](n), and [[Ag(dpppen)(CN-t-Bu)]BF(4)](n) have been synthesized and fully characterized as model materials for the mixed bridging ligand polymers which exhibit the general formula [[M(diphos)(dmb)]BF(4)](n) (M = Cu, Ag; dmb = 1,8-diisocyano-p-menthane) and [[Ag(dppm)(dmb)]ClO(4)](n). The identity of four polymers ([[Ag(dppb)(CN-t-Bu)(x)]BF(4)](n) (x = 1, 2), [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n), [[Ag(dppm)(dmb)]ClO(4)](n)) and the two dimers has been confirmed by X-ray crystallography. The structure of [[Ag(dppm)(dmb)]ClO(4)](n) exhibits an unprecedented 1-D chain of the type "[Ag(dmb)(2)Ag(dppm)(2)(2+)](n)", where d(Ag(.)Ag) values between tetrahedral Ag atoms are 4.028(1) and 9.609(1) A for the dppm and dmb bridged units, respectively. The [[Ag(dppb)(CN-t-Bu)(x)]BF(4)](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)](BF(4))(2)](n) polymer, which is produced from the rearrangement of [[Ag(dppb)(CN-t-Bu)(2)]BF(4)](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 micros. These emissions are assigned to a metal-to-ligand charge transfer (MLCT) of the type M(I) --> pi(NC)/pi(PPh(2)).

A new and convenient synthesis of the upper-rim monobrominated calix[4]arene Br-calixPR2 is reported and has been used as the key precursor for the preparation of both the diphenyl- (6a) and diisopropylphosphine ligands (6b). Reactions of these new ligands with [(C5Me5)RhCl2]2 afford the complexes (calixPR2)(C5Me5)Rh(Cl)2 (8a,b), which can be converted into their corresponding dihydrides (calixPR2)(C5Me5)Rh(H)2 (9a,b) using NaBH4. 6a also reacts with (C5Me5)Rh(CO)2 to form (calixPPh2)(C5Me5)Rh(CO) (10). The X-ray structures for both 8a and 8b confirm the cone geometry of the calix[4]arene bowl and reveal the presence of the phenyl and isopropyl groups over the cavity. With respect to the Rh−P bond, a gauche conformation is depicted in the solid state. Complexes 8a,b and 9a,b appear to be fluxional in solution, as demonstrated from VT 1H and 31P NMR measurements for 8a,b. Molecular modelings confirm the presence of 13 conformers associated with the rotation around the C(calix)−P and P−Rh bonds and the cavity locking groups above it. The minimum energy conformation for the unsaturated (calixPPh2)(C5Me5)Rh complex exhibits the Rh atom well located at the opening of the free cavity.

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