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

The potassium salts of H 2 NC(S)NHP(S)(O i Pr) 2 (HL I ) or o ‐C 6 H 4 [NHC(S)NHP(S)(O i Pr) 2 ] 2 (H 2 L II ) react with [Cu(PPh 3 ) 3 I] or a mixture of CuI and Ph 2 P(CH 2 ) 1–3 PPh 2 or Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 in aqueous EtOH/CH 2 Cl 2 to give mononuclear complexes [Cu(PPh 3 )L I ] ( 1 ), [Cu{Ph 2 P(CH 2 ) 2 PPh 2 }L I ] ( 2 ), [Cu{Ph 2 P(CH 2 ) 3 PPh 2 }L I ] ( 3 ) or [Cu{Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 }L I ] ( 4 ), or dinuclear complexes [Cu 2 (Ph 2 PCH 2 PPh 2 )L I 2 ] ( 5 ), [Cu 2 (PPh 3 ) 2 L II ] ( 6 ), [Cu 2 {Ph 2 P(CH 2 ) 2 PPh 2 } 2 L II ] ( 7 ), [Cu 2 {Ph 2 P(CH 2 ) 3 PPh 2 } 2 L II ] ( 8 ), [Cu 2 {Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 } 2 L II ] ( 9 ) or [Cu 2 (Ph 2 PCH 2 PPh 2 )L II ] ( 10 ). The structures of these compounds were investigated by 1 H and 31 P{ 1 H} NMR, UV/Vis spectroscopy and elemental analysis. The crystal structures of H 2 L II , 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.