Versatile structures and photophysical properties of poly- and mononuclear CuI complexes with N-thiophosphorylated thioureas RNHC(S)NHP(S)(OiPr)2 and phosphanes

Abstract

Reaction of the potassium salts of N-thiophosphorylated thioureas RNHC(S)NHP(S)(OiPr)₂ (R = Me, HL^II; 2-MeC₆H₄, HL^IIII; and 6-MePy-2, HL^III) with CuI in aqueous EtOH leads to the polynuclear complexes [CuL^I]_n (1), [Cu₃L^II₃] (2) and [Cu₄L^III₄] (3). Reaction of the potassium salts KL^II^–III–III–III with [Cu(PPh₃)₃I] or a mixture of CuI and Ph₂P(CH₂)_1–3PPh₂ or Ph₂P(C₅H₄FeC₅H₄)PPh₂ in aqueous EtOH/CH₂Cl₂ leads to the binuclear [Cu₂(Ph₂PCH₂PPh₂)L^II₂] (4) and [Cu₂(Ph₂PCH₂PPh₂)L^III₂] (5), or mononuclear [Cu(PPh₃)₂L^II,III] (6 and 7), [Cu{Ph₂P(CH₂)₂PPh₂}L^II,III] (8 and 9), [Cu{Ph₂P(CH₂)₃PPh₂}L^II,III] (10 and 11), [Cu{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^I–III] (12–14) complexes. The structures of these compounds were investigated by elemental analysis, ¹H, ³¹P{¹H} NMR and UV-Vis spectroscopy. The crystal structures of HL^III, 2, 3, 6 and 12 were determined by single-crystal X-ray diffraction. The luminescent properties of the complexes in the solid state are reported.