Preparation and Solid-State Characterization of Mixed-Ligand Coordination/Organometallic Oligomers and Polymers of Copper(I) and Silver(I) Using Diphosphine and Mono- and Diisocyanide Ligands

Abstract

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)).

Small Metal‐Containing Oligomers Using M2(dmpm)x and M2(dmb)y Luminescent Building Blocks (M = Cu, Ag; x = 2, 3; y = 1, 2)

“…The methodology has been tested on the X-ray data for 1, 2, and the related binuclear complex [Ag 2 (dppm) 2 (CNtBu) 2 ](ClO 4 ) 2 [17] (Table 4) in order to provide a degree of confidence in the results. The M···M and M···P distances are computed within an uncertainty of 0.05Ϫ0.06 Å , which is acceptable in the context of this work.…”

“…[1Ϫ14] In this respect, our group has recently reported the syntheses and characterizations of 1-D polymers of the type {M(dmb) 2 ϩ } n [15,16] and the mixed-ligand polymers {M 2 (dppm) 2 (dmb) 2 2ϩ } n [17] (M ϭ Cu, Ag; dmb ϭ 1,8-diisocyano-p-menthane in its U-or Z-conformation; dppm ϭ bis(diphenylphosphanyl)-methane; Scheme 1). The chromophores are the M(CϵNR) 4 ϩ centers (M ϭ Cu, Ag), which are separated by 5 Å (Ag···Ag distance) in {Ag(dmb) 2 ϩ } n , [15] and the M(CϵNR) 2 (P) 2 ϩ units, which are separated by 4.03 and 9.61 Å in {Ag 2 (dppm) 2 (dmb) 2 2ϩ } n .…”

“…The chromophores are the M(CϵNR) 4 ϩ centers (M ϭ Cu, Ag), which are separated by 5 Å (Ag···Ag distance) in {Ag(dmb) 2 ϩ } n , [15] and the M(CϵNR) 2 (P) 2 ϩ units, which are separated by 4.03 and 9.61 Å in {Ag 2 (dppm) 2 (dmb) 2 2ϩ } n . [17] The average polymer length for the {Ag(dmb) 2 ϩ } n materials in solution was determined to be approximately 8 units by T 1 /NOE measurements, [18] whereas the amorphous Cu analogue had an average polymer length of 300 units, as determined by light scattering. [15] This difference is explained by the greater lability of the dmb ligand in the Ag I complexes, which was convincingly verified by the interconversion observed between the U-and Z-isomers of the {Ag(dmb) 2 ϩ } n polymers, but not for the Cu analogues.…”

Crystal structure of bis(µ2-1,3-bis(diphenylphosphino)propane-κ2P,P')- bis(acetato-κ2O,O')disilver(I)-methanol (1:4), [Ag2(CH3COO)2(C27H26P2)2]·4CH3OH, C62H74Ag2O8P4

“…The coordination chemistry of silver(I) complexes with diphosphine ligands has been extensively studied [1][2][3][4][5]. We are interested in synthesizing new Ag(I) complexes containing diphosphine ligands and isoquinoline.…”

Synthesis and Characterization of Linear Tetranuclear Silver(I) Complexes Bridged by Tetraphosphane Ligands

“…[18] However, discrete silver(I) complexes that has more than three silver(I) ions with isocyanide ligands have never been reported. To expand this chemistry, we attempted to introduce isocyanide ligands into the {Ag 4 (µ-dpmppm) 2 } 4+ core.…”