Pt(II) and Pd(II)-assisted coupling of nitriles and 1,3-diiminoisoindoline : Synthesis and luminescence properties of (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) and Pd(II) complexes

Abstract

Treatment of trans-[PtCl2(NCR)2] 1 (R = Me (1a), Et (1b), o-ClC6H4 (1c), p-ClC6H4 (1d), p-(HCdouble bond; length as m-dashO)C6H4 (1e), p-O2NC6H4CH2 (1f)) with 1,3-diiminoisoindoline HNdouble bond; length as m-dashCC6H4C(NH)double bond; length as m-dashNH 2 gives access to the corresponding (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) complexes [PtCl{NHdouble bond; length as m-dashC(R)Ndouble bond; length as m-dashC(C6H4)NCdouble bond; length as m-dashNC(R)double bond; length as m-dashNH}] 3a–f, in good yields (65–70%). The reaction of trans-[PdCl2(NCMe)2] 4a with 2 furnishes (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pd(II) complex [PdCl{NHdouble bond; length as m-dashC(Me)Ndouble bond; length as m-dashC(C6H4)NCdouble bond; length as m-dashNC(Me)double bond; length as m-dashNH}] 5a, in good yield (65%). However, the reaction of trans-[PdCl2(NCR)2] 4 (R = Ph (4b), p-MeC6H4CH2 (4c), p-(HCdouble bond; length as m-dashO)C6H4 (4d), p-O2NC6H4CH2 (4e)) with 2 gives a number of unidentified products. The compounds 3a–f and 5a were characterized by IR, 1H, 13C and DEPT-135 NMR spectroscopies, elemental analyses and, in the case of the Pt(II) complex [PtCl{NHdouble bond; length as m-dashC(Me)Ndouble bond; length as m-dashC(C6H4)NCdouble bond; length as m-dashNC(Me)double bond; length as m-dashNH}] 3a, also by X-ray diffraction analysis. Compounds 3a and 3b were also characterized by UV–Vis absorption and luminescence emission spectroscopies. Emission quantum yields of ca. 3 × 10−3 were obtained in dichloromethane solution, and luminescence lifetimes are in the order of the tens of nanoseconds. Both compounds also exhibited luminescence in solid state (polystyrene matrix), with luminescence lifetimes in the order of hundreds of nanoseconds.