Structural Variations and Spectroscopic Properties of Luminescent Mono- and Multinuclear Silver(I) and Copper(I) Complexes Bearing Phosphine and Cyanide Ligands

Abstract

Reaction of equimolar amounts of AgCN and PCy3 gave the polymer [(Cy3P)Ag(NCAgCN)]infinity (1), whereas employment of excess PCy3 yielded the discrete compound [(Cy3P)2Ag(NCAgCN)] (2). Reacting bis(dicyclohexylphosphino)methane (dcpm) with AgCN in 1:1 and 1:2 molar ratios gave two crystalline forms, namely [Ag2(mu-dcpm)2][Ag(CN)2]2 x (CH3OH)2 (3a x (CH3OH)2) and [Ag2(mu-dcpm)2][Ag(CN)2]2 (3b), respectively. The similar reaction of CuCN with PCy3 afforded the polymeric compound [{(Cy3P)Cu(CN)}3]infinity (4), whereas treatment of CuCN with dcpm gave [Cu2(mu-dcpm)2(CN)2] (5). Employment of diphosphine ligands with longer -(CH2)n- spacers, such as 1,2-bis(dicyclohexylphosphino)ethane (dcpe, n = 2) and 1,3-bis(diphenylphosphino)propane (dppp, n = 3), in reactions with [Cu(CH3CN)4]PF6 and KCN afforded the macrocylic compounds [{Cu(dcpe)}2(CN)(mu-dcpe)]PF6 (6(PF6)) and [{Cu(dppp)}3(CN)2(mu-dppp)]PF6 (7(PF6)), respectively. The hexanuclear complex [Cu(CN)(PCy3)]6 (8) was obtained by reacting CuCN with PCy3 in the presence of sodium pyridine-2-thiolate. The UV-vis absorption spectrum of 1 in acetonitrile displays a weak shoulder at 245 nm (epsilon = 350 dm3 mol(-1) cm(-1)). For 3a, 3b, and 5, the intense absorption bands at lambdamax = 257-276 nm with epsilon values of (1.73-1.80) x 10(4) dm3 mol(-1) cm(-1) are assigned to [ndsigma --> (n + 1)psigma] transitions. Complexes 3a and 3b emit at lambdamax = 365 nm in CH3CN (quantum yield approximately 6 x10(-3), lifetime approximately 0.2 micros). The solid-state emission of 5 (lambdamax = 470 and 488 nm at 298 and 77 K) is red-shifted in energy from that of 4 (lambdamax = 401 and 405 nm at 298 and 77 K, respectively). In 77 K MeOH/EtOH (1:4) glassy solution, complexes 4-8 display intense emission with lambdamax at 382-416 nm, which is assigned to the [3d --> (4s, 4p)] triplet excited state.

Cyanide‐Assembled d10Coordination Polymers and Cycles: Excited State Metallophilic Modulation of Solid‐State Luminescence

“…The XRD structurala nalysis reveals zig-zag patterns of the polymer chains for 1 and 3-5,r eminiscent of [(Cy 3 P)Cu(CN)] n [18] and [(Ph 3 P) 2 M{M'(CN) 2 }] n…”

Structure and Bonding in Copper(I) Carbonyl and Cyanide Complexes

“…Only one compound of this type is constructed solely from monodentate ligands: (1-MeIm)3CuCN 43. Species XII and XIII are unique examples of neutral 3-and 2-coordinate CuCN complexes.51b,55 In XII the trigonal angle sum is a nearly planar value of 359.5°, and in XIII the Species XIV exhibits a cuprophilic interaction supported by the bridging diphosphine with a Cu … Cu distance of 2.940(1) Å 56. The Mo-Cu cation XV is another example of a Cu(I) cubane.…”

Crystal structure of μ-cyanido-1:2κ2N:C-dicyanido-1κC,2κC-bis(quinolin-8-amine-1κ2N,N′)-2-silver(I)-1-silver(II): rare occurrence of a mixed-valence AgI,IIcompound

“…It has been used not only as a counter-ion (e.g. Stork et al, 2005) but also as a ligand for numerous transition-metal ions, including Ag + (Lin et al, 2005).…”