Inorganic Chemistry, Vol.41, No.8, 2275-2281, 2002
Synthesis, structures, and emissive properties of platinum(II) complexes with a cyclometallating aryldiamine ligand
A new series of square planar Pt(II) complexes with the mer-coordinating tridentate ligand, PiP(2)NCN(-) (pip(2)NCNH = 1,3-bis(piperdylmethyl)benzene), has been prepared: Pt(PiP(2)NCN)Cl (2), Pt(PiP(2)NCN)Br (3), Pt(pip(2)NCN)I (4), and [Pt(pip(2)NCN)(CH3N=C(CH3)(2))][CF3SO3] (5). The complexes have been fully characterized by H-1 NMR spectroscopy, elemental analysis, and UV-vis spectroscopy. The X-ray crystal structures Of pip(2)NCNBr (1), 2, and 5 are reported. Compound 1: triclinic, P (1) over bar, a = 10.081(1) Angstrom, b = 10.153(2) Angstrom, c = 10.390(1) Angstrom, alpha = 66.05(1)degrees, beta = 79.07(1)degrees, gamma = 64.51 (1)degrees, V = 877.1(2) Angstrom(3), Z = 2. Complex 2: triclinic, P (1) over bar, a = 9.897(2) Angstrom, b = 10.191(2) Angstrom, c = 19.174(4) Angstrom, alpha = 75.09(3)degrees, alpha = 76.14(3)degrees, gamma = 71.00(3)degrees, V = 1741.2(6) Angstrom(3), Z = 4. Complex 5: triclinic, P (1) over bar, a = 10.709(2) Angstrom, b = 11.2321 (10) Angstrom, c = 12.447(2) Angstrom, alpha = 110.509(8)degrees, beta = 112.417(10)degrees, gamma = 91.066(9)degrees, V = 1276.1(3) Angstrom(3), Z = 2. In 77 K 3:1 EtOH/MeOH glassy solution, these colorless complexes exhibit weak red-orange to red emissions originating from a lowest spin-forbidden ligand field excited state.