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Relevant academic research and scientific papers

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

Treatment of trans-[PtCl2(NCR)2] 1 (R?=?Me (1a), Et (1b), o-ClC6H4 (1c), p-ClC6H4 (1d), p-(HC[dbnd]O)C6H4 (1e), p-O2NC6H4CH2 (1f)) with 1,3-diiminoisoindoline HN[dbnd]CC6H4C(NH)[dbnd]NH 2 gives access to the corresponding (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) complexes [PtCl{NH[dbnd]C(R)N[dbnd]C(C6H4)NC[dbnd]NC(R)[dbnd]NH}] 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{NH[dbnd]C(Me)N[dbnd]C(C6H4)NC[dbnd]NC(Me)[dbnd]NH}] 5a, in good yield (65%). However, the reaction of trans-[PdCl2(NCR)2] 4 (R?=?Ph (4b), p-MeC6H4CH2 (4c), p-(HC[dbnd]O)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{NH[dbnd]C(Me)N[dbnd]C(C6H4)NC[dbnd]NC(Me)[dbnd]NH}] 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.

A new family of luminescent compounds: Platinum(II) imidoylamidinates exhibiting pH-dependent room temperature luminescence

The imidoylamidinate platinum(II) compounds [Pt{NH=C(R)NC(Ph)=NPh} 2] (R = CH2Ph 2, p-ClC6H4 3, Ph 4) were prepared by the reaction of the appropriate trans-[PtCl 2(RCN)2] with 4 equiv of the amidine PhC(=NH)NHPh giving 2-4 and 2 equivs of the salt PhC(=NH)NHPh·HCl. We also synthesized, by the double alkylation of 4 with MeOSO2CF3, complex [Pt{NH=C(Ph)N(Me)C(Ph)=NPh}2][CF3SO3] 2 (5) which models the bis-protonated form of 4. The complexes were characterized by 1H, 13C NMR, and IR spectroscopies, FAB-MS and by C, H, N elemental analysis. The X-ray crystallography of 4·2CH2Cl2 enables the confirmation of the square planar coordination geometry of the metal center with almost planar imidoylamidine ligands, while in 5·2CHC3 the planarity of the metallacycles is lost and and the central N atom is sp3-hybridized. The imidoylamidinate complexes represent a new family of Pt(II)-based luminescent complexes and they are emissive at room temperature both in solution and in the solid state, with an emission quantum yield ranging from 3. 7 × 10-4 to 6.2 × 10-2 in methanol solution; the emission intensity is pH-dependent, being quenched at low pH. UV-visible and luminescence spectroscopies indicate that the lowest excited state of these compounds is 3MLCT or 3IL with significant MLCT character, with emission lifetimes of a few μs. A blue shift of both the absorption and emission with increasing solvent polarity and with decreasing π-electron withdrawing properties of the ligand substituent was observed. The Royal Society of Chemistry 2006.