A Novel Catenarian Cyano(triphenyl phosphite) Copper(I) Complex: Synthesis, Crystal Structure, Thermal, Voltammetric and Spectral Properties^†

Abstract

Quantitative reaction between copper(I) cyanide and triphenyl phosphite forms copper(I) complex [(P(OPh) 3 ) 4 Cu 4 (CN) 4 ] (1). X-Ray crystal structure shows a catenarian polymer of tandem interconnected copper cyanide, with C and N connecting to proximal Cu atoms. The Cu atoms adopt two different conformations: one exhibits linear construction, while the other exhibits distorted tetrahedral geometry through coordinating to two cyano groups and the P donors of triphenyl phosphite molecules. The feature of 1 is the propagation pattern of two-and four-coordination along with the chain. IR and electronic absorption spectra also confirm the established single crystal structure. Thermal analysis indicates that 1 has a high thermal stability. 3-D fluorescence result shows the middle absorption peaks with the maximum excitement and emission wavelength 342 and 350 nm, respectively. Cyclic voltammogram in DMSO, DMF and MeCN gives a midpoint voltage of -0.003, 0.061 and 0.137 V versus SCE, respectively, showing the different solvent virtue on reduction potential.

Copper phthalocyanine films deposited by liquid–liquid interface recrystallization technique (LLIRCT)

“…The redox behavior of metal is due to interaction between cocoordinating symmetrical organic molecules with central copper metal [15][16][17]. Fig.…”

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

“…Multidentate ligands produce a range of stoichiometries and network structures that is too large to tackle here. ,,,, As an example, let us consider the complexes of CuCN with the potentially tetradentate, adamantane-like HTMA ligand. , Three phases are known: (CuCN) 3 (HMTA) 2 , (CuCN) 5 (HMTA) 2 , and (CuCN) 5 (HMTA) (see Figure ). These correspond to bi-, tri-, and tetradentate bridging modes of HMTA.…”

Theoretical insights into the effect of amine and phosphine decoration on the photoluminescence of copper(i) and silver(i) coordination polymers

“…{Ag,Cu}CN(PAr 3 ) materials have been reported. 27,28 Fewer examples of ligand-rich (M:L < 1:1) and ligand-deficient (M:L > 1:1) materials have been synthesized. The former tend to be found for L = aromatic amine or mixed phosphine/aromatic amine due to the low stabilization energy for coordination of a fourth ligand to Cu(I).…”

“…[8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] For decorated Cu(I) networks, the metal centres tend to be three-coordinate with one ligand bonded to each metal centre, although examples of alternating 2/4-coordination of CuCN(P(OPh) 3 ), AgCN(PAr 3 ) and {Ag,Cu}CN(PAr 3 ) materials have been reported. 27,28 Fewer examples of ligand-rich (M : L < 1 : 1) and ligand-deficient (M : L > 1 : 1) materials have been synthesized. The former tend to be found for L = aromatic amine or mixed phosphine/aromatic amine due to the low stabilization energy for coordination of a fourth ligand to Cu(I).…”