Synthesis, characterization and luminescent properties of heteroligand copper(I) complexes with N-thiophosphorylated thioureas RNHC(S)NHP(S)(OiPr)2 (R = iPr, tBu, Ph, 2,6-Me2C6H3, 2,4,6-Me3C6H2) and phosphines (PPh3, Ph2P(C5H4FeC5H4)PPh2)

Reaction of the potassium salts of RNHC(S)NHP(S)(OiPr)2 (R = iPr, HLI; tBu, HLII; Ph, HLIII; 2,6-Me2C6H3, HLIV; 2,4,6-Me3C6H2, HLV) with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to mononuclear [Cu(PPh3)2LII] (1), [Cu(PPh3)2LV] (2), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (3), [Cu{Ph2P(C5H4FeC5H4)PPh2}LII] (4), [Cu{Ph2P(C5H4FeC5H4)PPh2}LIII] (5), [Cu{Ph2P(C5H4FeC5H4)PPh2}LIV] (6) and [Cu{Ph2P(C5H4FeC5H4)PPh2}LV] (7) complexes. The structures of these complexes were investigated by 1H, 31P{1H} NMR spectroscopy and elemental analysis. The crystal structures of 1, 2 and 4 were determined by single crystal X-ray diffraction. The complexes 3–7 exhibit emission in the solid state at ambient temperature that might be explained by the presence of the ferrocene-diyl unit in the chelate phosphine.

Graphical abstractReaction of the potassium salts of RNHC(S)NHP(S)(OiPr)2 (R = iPr, HLI; tBu, HLII; Ph, HLIII; 2,6-Me2C6H3, HLIV; 2,4,6-Me3C6H2, HLV) with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to mononuclear [Cu(PPh3)2LII] (1), [Cu(PPh3)2LV] (2), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (3), [Cu{Ph2P(C5H4FeC5H4)PPh2}LII] (4), [Cu{Ph2P(C5H4FeC5H4)PPh2}LIII] (5), [Cu{Ph2P(C5H4FeC5H4)PPh2}LIV] (6) and [Cu{Ph2P(C5H4FeC5H4)PPh2}LV] (7) complexes. The crystal structures of 1, 2 and 4 were determined by single crystal X-ray diffraction. The complexes 3–7 exhibit emission in the solid state at ambient temperature that might be explained by the presence of the ferrocene-diyl unit in the chelate phosphine.Figure optionsDownload full-size imageDownload as PowerPoint slide