Heteroligand copper(I) complexes of N-thiophosphorylated thioureas and phosphanes: Versatile structures and luminescence

Reaction of the potassium salts of (EtO)2P(O)CH2C6H4-4-(NHC(S)NHP(S)(OiPr)2) (HLI), (CH2NHC(S)NHP(S)(OiPr)2)2 (H2LII) or cyclam(C(S)NHP(S)(OiPr)2)4 (H4LIII) with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to [Cu(PPh3)LI] (1), [Cu2(Ph2PCH2PPh2)2LII] (2), [Cu{Ph2P(CH2)2PPh2}LI] (3), [Cu{Ph2P(CH2)3PPh2}LI] (4), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (5), [Cu2(PPh3)2LII] (6), [Cu2(Ph2PCH2PPh2)LII] (7), [Cu2{Ph2P(CH2)2PPh2}2LII] (8), [Cu2{Ph2P(CH2)3PPh2}2LII] (9), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (10), [Cu8(Ph2PCH2PPh2)8LIIII4] (11), [Cu4{Ph2P(CH2)2PPh2}4LIII] (12), [Cu4{Ph2P(CH2)3PPh2}4LIII] (13) or [Cu4{Ph2P(C5H4FeC5H4)PPh2}4LIII] (14) complexes. The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopy; their compositions were examined by microanalysis. The luminescent properties of the complexes 1–14 in the solid state are reported.

Reaction of the potassium salts of (EtO)2P(O)CH2C6H4-4-(NHC(S)NHP(S)(OiPr)2) (HLI), (CH2NHC(S)NHP(S)(OiPr)2)2 (H2LII) or cyclam(C(S)NHP(S)(OiPr)2)4 (H4LIII) with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to [Cu(PPh3)LI] (1), [Cu2(Ph2PCH2PPh2)2LII] (2), [Cu{Ph2P(CH2)2PPh2}LI] (3), [Cu{Ph2P(CH2)3PPh2}LI] (4), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (5), [Cu2(PPh3)2LII] (6), [Cu2(Ph2PCH2PPh2)LII] (7), [Cu2{Ph2P(CH2)2PPh2}2LII] (8), [Cu2{Ph2P(CH2)3PPh2}2LII] (9), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (10), [Cu8(Ph2PCH2PPh2)8LIIII4] (11), [Cu4{Ph2P(CH2)2PPh2}4LIII] (12), [Cu4{Ph2P(CH2)3PPh2}4LIII] (13) or [Cu4{Ph2P(C5H4FeC5H4)PPh2}4LIII] (14) complexes.Figure optionsDownload as PowerPoint slideHighlights
► We synthesize mixed-ligand Cu(I) complexes of N-thiophosphorylthioureas and phosphines.
► We study luminescence properties of the obtained complexes.
► All complexes, containing bisphosphine ligands, show luminescence in the solid state.