Platinum(II) complexes with pi-conjugated, naphthyl-substituted, cyclometalated ligands (RC N N): structures and photo- and electroluminescence.

The crystal structures and photophysical properties of mononuclear [(RC N N)PtX](ClO4)n ((RC N N)=3-(6'-(2''-naphthyl)-2'-pyridyl)isoquinolinyl and derivatives; X=Cl, n=0; X=PPh(3) or PCy(3), n=1), dinuclear [(RC N N)2Pt2(mu-dppm)](ClO4)2 (dppm=bis(diphenyphosphino)methyl) and trinuclear [(RC N N)3Pt3(mu-dpmp)](ClO4)3 (dpmp=bis(diphenylphosphinomethyl)phenylphosphine) complexes are presented. The crystal structures show extensive intra- and/or intermolecular pipi interactions; the two (RC N N) planes of [(RC N N)2Pt2(mu-dppm)](ClO4)2 (R=Ph, 3,5-tBu2Ph or 3,5-(CF3)2Ph) are in a nearly eclipsed configuration with torsion angles close to 0 degrees. [(RC N N)PtCl], [(RC N N)2Pt2(mu-dppm)](ClO4)2, and [(RC N N)3Pt3(mu-dpmp)](ClO4)3 are strongly emissive with quantum yields of up to 0.68 in CH2Cl2 or MeCN solution at room temperature. The [(RC N N)PtCl] complexes have a high thermal stability (T(d)=470-549 degrees C). High-performance light-emitting devices containing [(RC N N)PtCl] (R=H or 3,5-tBu2Ph) as a light-emitting material have been fabricated; they have a maximum luminance of 63,000 cd m(-2) and CIE 1931 coordinates at x=0.36, y=0.54.

Borazine materials for organic optoelectronic applications.

Borazine materials have been demonstrated to be a new class of multifunctional and thermally stable materials with high electron (10(-3) cm2 V(-1) s(-1)) and moderate hole (10(-4) cm2 V(-1) s(-1)) mobilities for applications in electroluminescent devices.

[(O--N--N)PtX] complexes as a new class of light-emitting materials for electrophosphorescent devices.

The synthesis and photophysical properties of the robust Pt(II) emitters [(O--N--N)PtX] (HO--N--N = 6-(2-hydroxyphenyl)-2,2'-bipyridine and its derivatives; X = Cl, Br, I, or -CC-Ph) are reported. Yellow electroluminescent devices based on these materials display a low turn-on voltage (1 cd m(-2) at 4 V) and a high luminance (37000 cd m(-2)). Complex 2e, [(F(t)Bu2O--N--N)PtCl], has the highest thermal stability and gave the best OLED.

Homoleptic, sigma-bonded octahedral [M(CO)(6)](2+) cations of iron(II), ruthenium(II), and osmium(II). Part 1: Syntheses, thermochemical and vibrational characterizations, and molecular structures as [Sb(2)F(11)](-) and [SbF(6)](-) salts. A comprehensive, comparative study.

Homoleptic octahedral, superelectrophilic sigma-bonded metal carbonyl cations of the type [M(CO)(6)](2+) (M = Ru, Os) are generated in the Bronsted-Lewis conjugate superacid HF/SbF(5) by reductive carbonylation of M(SO(3)F)(3) (M = Ru, Os) or OsF(6). Thermally stable salts form with either [Sb(2)F(11)](-) or [SbF(6)](-) as anion, just as for the previously reported [Fe(CO)(6)](2+) cation. The latter salts are generated by oxidative (XeF(2)) carbonylation of Fe(CO)(5) in HF/SbF(5). A rationale for the two diverging synthetic approaches is provided. The thermal stabilities of [M(CO)(6)][SbF(6)](2) salts, studied by DSC, range from 180 degrees C for M = Fe to 350 degrees C for M = Os before decarbonylation occurs. The two triads [M(CO)(6)][SbF(6)](2) and [M(CO)(6)][Sb(2)F(11)](2) (M = Fe, Ru, Os) are extensively characterized by single-crystal X-ray diffraction and vibrational and (13)C NMR spectroscopy, aided by computational studies of the cations. The three [M(CO)(6)][SbF(6)](2) salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereas the corresponding [Sb(2)F(11)](-) salts are monoclinic, crystallizing in space group P2(1)/n (No. 14). In both triads, the unit cell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF(6)](-) and [Sb(2)F(11)](-) and their vibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational properties of the [M(CO)(6)](2+) cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independent of M and nearly identical. Interionic C...F contacts are similarly weak in all six salts. Metal dependency is noted only in the (13)C NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-O stretching fundamentals (A(1g) and T(1u)). The findings reported here are unprecedented among metal carbonyl cations and their salts.

Self-assembled zinc(II) Schiff base polymers for applications in polymer light-emitting devices.

Thermally stable zinc(II) Schiff base polymers (decomposition temperature up to 461 degrees C; M(n)= 13580 to 20440) formed by self-assembly reactions of zinc(II) salts and salicylaldimine monomers exhibit blue to yellow PL with quantum yields up to 0.34 in DMF; PLEDs employing these polymers as emitters give green or orange EL with turn-on voltage at 5 and 6 V and maximum efficiency of 2.0 and 2.6 cd A(-1) respectively.

Self-aggregated phosphorescent platinum(II) polymeric material from modified poly(4-vinylpyridine).

A solvochromic material made from incorporation of photoluminescent Pt(II)([formula: see text]) moieties into commercially available homopolymer poly(4-vinylpyridine) exhibits different emission energies, due to different degrees of self-aggregation in various solvents and as thin film upon exposure to vapour of different volatile organic compounds (VOC); self-aggregation enables intra- and intermolecular interactions arising from pi-stacking of the Pt([formula: see text]) moieties, which is affected by medium polarity.

Synthesis and Structure of [{Mo(CO)(4)}(2)(cis-&mgr;-F(2)SbF(4))(3)](x)()[Sb(2)F(11)](x)(): An Ionic Coordination Polymer.

The oxidation of molybdenum hexacarbonyl, Mo(CO)(6), by antimony(V) fluoride, SbF(5), at 60 degrees C in an excess of liquid SbF(5), produces polymeric [{Mo(CO)(4)}(2)(cis-&mgr;-F(2)SbF(4))(3)](x)()[Sb(2)F(11)](x)() as the main product. Recrystallization from HF-SbF(5) produces orange prismatic crystals, suitable for a single-crystal X-ray diffraction study. Crystals of [{Mo(CO)(4)}(2)(cis-&mgr;-F(2)SbF(4))(3)](x)()[Sb(2)F(11)](x)() are monoclinic, space group P2(1)/c (No. 14), a = 9.234(4) Å, b = 13.858(3) Å, c = 25.790(3) Å, beta = 90.532(2) degrees, V = 3300.1(12) Å(3), and Z = 4. The structure was solved by the Patterson method and refined with anisotropic thermal parameters to R = 0.048 and R(w)() = 0.047 (on F, 472 variables, 5116 observations with I >/= 3sigma(I)). In the polymeric cation, two pyramidal Mo(CO)(4) groups are linked by bridging, iso-bidentate F(2)SbF(4) groups first into eight-membered rings, which are then further linked into polymeric chains. The bridging F(2)SbF(4) groups and the [Sb(2)F(11)](-) anion are involved in significant intermolecular and interionic F.C contacts to the C atoms of the Mo(CO)(4) groups.