A cyclometalated dinuclear platinum(II) complex bridged with pyridine-2-thiolate ions, [Pt2(ppy)2(pyt)2] (Hppy = 2-phenylpyridine, Hpyt = pyridine-2-thiol) and its oxidized platinum(III) complex, [Pt2Cl2(ppy)2(pyt)2] have been synthesized and characterized. The divalent complex exhibits intense red luminescence both in solution and in the solid states. Corresponding to the short Pt···Pt distance (2.849(1) Å) for [Pt2(ppy)2(pyt)2], the reversible conversion between the divalent and trivalent complexes occurs easily with appearance and disappearance of the luminescence.
Dicyano(4,4′-dicarboxy-2,2′-bipyridine)platinum(II) forms pH-dependent polymorphs of various colors and displays outstanding vapochromism followed by luminescence changes upon exposure to certain organic vapors. The high sensitivity of the complex to vapor and pH is related to its three-dimensional network structure, which includes large cavities formed by hydrogen bonds and Pt···Pt interactions.
Electroluminescent properties of an emissive binuclear platinum(II) complex have been studied. We fabricated organic light-emitting diodes based on Pt2(ppy)2(pyt)2 (ppy = 2-phenylpyridine, pyt = pyridine-2-thiolate) phosphor, which exhibits an emission from a 3MMLCT state based on a Pt-Pt interaction. An electrophosphorescent device with a multilayer configuration of ITO/CuPc/NPB/Pt2(ppy)2(pyt)2/BAlq/Alq3/LiF/Al demonstrated red emission with Commission Internationale de L'Eclairage (CIE) coordinates of x=0.65, y=0.35, a maximum luminous efficiency of 1.8 cd/A (1.0 mA/cm2), and an external quantum efficiency of 3.4%.
The title Pt(II) complexes, viz. (2,2'-bipyridine-kappa(2)N,N')[(1R,2R)-1,2-diaminocyclohexane-kappa(2)N,N']platinum(II) bis(hexafluorophosphate), [Pt(C(6)H(14)N(2))(C(10)H(8)N(2))](PF(6))(2), and [(1R,2R)-1,2-diaminocyclohexane-kappa(2)N,N'](1,10-phenanthroline-kappa(2)N,N')platinum(II) bis(hexafluorophosphate), [Pt(C(6)H(14)N(2))(C(12)H(8)N(2))](PF(6))(2), containing an aromatic alpha-diimine and a non-planar diaminocyclohexane, both form a ladder-type structure, which is constructed via loose pi-pi stacking on the alpha-diimine ligands and hydrogen bonding between the cyclic amines and the counter-anions. In the former compound, there are two independent complex cations, both of which have a twofold axis through the Pt atom.
The title dinuclear platinum(III) complex, [Pt2(C11H8N)2(C5H4NS)4], forms two crystal structures, viz. the non-solvated and acetonitrile-solvated (C2H3N) forms. For both forms, two (2-pyridylphenyl)platinum units are bridged by two pyridine-2-thiolate (pyt) anions in a head-to-tail configuration, and the other two pyridine-2-thiolate anions occupy the axial position, coordinated through their S atoms. The most remarkable difference between the two forms is the orientation of the axial monodentate ligands. Those for the solvated form are located over the 2-pyridylphenyl ligands, being related by a twofold axis which lies through the centre of the Pt-Pt bond, while the axial pyt ligands for the non-solvated form are oriented irregularly, which is attributable to the dimeric arrangement in the crystal.
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