Synthesis, Characterisation and Luminescent Properties of Mixed‐Ligand Copper(I) Complexes Incorporating N‐Thiophosphorylated Thioureas and Phosphane Ligands

Abstract

The potassium salts of H2NC(S)NHP(S)(OiPr)2 (HLI) or o‐C6H4[NHC(S)NHP(S)(OiPr)2]2 (H2LII) react with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 to give mononuclear complexes [Cu(PPh3)LI] (1), [Cu{Ph2P(CH2)2PPh2}LI] (2), [Cu{Ph2P(CH2)3PPh2}LI] (3) or [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (4), or dinuclear complexes [Cu2(Ph2PCH2PPh2)LI2] (5), [Cu2(PPh3)2LII] (6), [Cu2{Ph2P(CH2)2PPh2}2LII] (7), [Cu2{Ph2P(CH2)3PPh2}2LII] (8), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (9) or [Cu2(Ph2PCH2PPh2)LII] (10). The structures of these compounds were investigated by 1H and 31P{1H} NMR, UV/Vis spectroscopy and elemental analysis. The crystal structures of H2LII, 1, 3–6, 8 and 10 were determined by single‐crystal X‐ray diffraction. The luminescent properties of complexes 1–10 in the solid state are reported.

Synthesis and characterization of silver(I) complexes with N‐thiophosphorylated thiobenzamide or thiourea and phosphines

“…A reaction of the potassium salts of HL [17]. Unfortunately, after numerous attempts we were not successful to get X-ray suitable crystals, neither 1 and 5 nor 2-4 and 6-8.…”

“…The signals for the phosphine phosphorus atoms in the 31 P{ 1 H} NMR spectra of the complexes 1-8 exhibit chemical shifts ranging from −21.2 to −0.7 ppm [7,17].…”

“…Absorption maxima at around 300 nm and emissions around 450-510 nm are typical of Cu(I)-P and Ag(I)-P containing chromophores with either ILCT (σ −a π ) or MLCT (d-σ *) excited states [7,17,19,[20][21][22]. Therefore, we can rather safely assign the absorption spectra of the complexes to ILCT (σ −a π ) or MLCT (d−σ *) in the Ag-PR 2 chromophore (the ILCT assignment is more probable), whereas a S(thiolate) → Ag(I) LMCT is very unlike in view of the d 10 configuration of the silver atoms.…”

Crystal structure of μ-1,4-bis(diphenylphosphine)butane-2,9-dimethyl-1,10-phenanthroline-κ2 N:N′-bis(cyano-κC)dicopper(I)]-water, C58H56Cu2N6O2P2

“…Mononuclar and binuclear copper(I) complexes containing diphosphine and N-heterocyclic ligands have been the focus of several investigations in the last few years because of their luminescence properties, interesting structures and novel reactivity performances [3][4][5]. During our previous work, a number of mixed-ligand coordination compounds of copper(I) salts with heterocyclic nitrogen ligands and diphosphanes were prepared and structurally characterized [6,7].…”

Synthesis and structural characterization of five new copper (I) complexes with 1,10-phenanthroline and 1,4-bis(diphenylphosphino)butane(dppb)

“…Especially heteroleptic Cu(I) compounds containing phosphines and N-donor ligands attract much attention due to their low cost, nontoxicity and luminescence [1][2][3][4][5][6][7][8]. Among them mononuclear and binuclear Cu(I) complexes containing diphosphine ligands and nitrogen ligands have been the focus of much investigation [9][10][11]. In 2009, Fu and his coworkers reported http://dx.doi.org/10.1016/j.molstruc.2014.12.068 0022-2860/Ó 2015 Elsevier B.V. All rights reserved.…”