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

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.