A multifunctional iridium carbazolyl orange phosphor for high performance two-element WOLED exploiting exciton-managed fluorescence/phosphorescence

By attaching a bulky, inductively electron-with drawing trifluoromethyl (CF3) group on the pyridyl ring of the rigid 2-[3(N-phenylcarbazolyl)]pyridine cyclometalated ligand, we successfully synthesized a new heteroleptic orange-emitting phosphorescent iridium(III) complex [Ir(L-1)(2)(acac)] 1 (HL1=5-trifluoromethyl-2-[3-(N-phenylcarbazolyl)]pyridine, Hacac = acetylacetone) in good yield.

Multifunctional metallophosphors with anti-triplet–triplet annihilation properties for solution-processable electroluminescent devices

With the goal to provide organometallic triplet emitters with good hole-injection/hole-transporting properties, highly amorphous character for simple solution-processed organic light-emitting diodes, and negligible triplet-triplet (T-T) annihilation, a series of new phosphorescent cyclometalated Ir-III and Pt-II complexes with triphenylamine-anchored fluorenylpyridine dendritic ligands were synthesized and characterized. The photophysical, thermal, electrochemical and electroluminescent properties of these molecules are reported.

Bis(2,2 '-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10] phenanthroline)ruthenium: Synthesis and electrochemical and electrochemiluminescence characterization

In this work, an electrochemiluminescence (ECL) reagent bis(2,2'-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10]phenanthroline)ruthenium complex (Ru-1) was synthesized, and its electrochemical and ECL properties were characterized. The synthesis of Ru-1 was confirmed by IR spectra, element analysis, and H-1 NMR spectra. For further study, its UV-vis absorption and fluorescence emission spectra were investigated. Ru-1 also exhibited quasi-reversible Ru-II/Ru-III redox waves in acetonitrile solution. The aqueous ECL behaviors of Ru-1 were also studied in the absence and in the presence of tripropylamine.

Novel Re(I) dendrimers: synthesis, characterization and theoretical studies

Four novel diimine rhenium(I) carbonyl complexes with the formula [Re(CO)(3)(L) Br], where L = 2-(4-(9H-carbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (P1), 2-(4-(3,6-di-tert-butyl-9H-carbazol-9-yl) phenyl)-1H-imidazo-[4,5-f][1,10] phenanthroline (P2), 2-(4-(6-(9H-carbazol-9-yl)-9H-3,9'-bicarbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (D1), and 2-(4-(3', 6'-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-9H-3,9'-bicarbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (D2), have been successfully synthesized and fully characterized by (HNMR)-H-1, IR, and UV-Vis, etc. The luminescence quantum yields (LQYs) of the parent Re(I) complexes P1 and P2 are 0.13 and 0.16, respectively, which are much higher than the previously reported Re(I) dendrimers. The HOMOs and the LUMOs of P1 and P2 are calculated to be mainly composed of [d(Re) + pi(CO + Br)] and pi*(L) orbital, respectively.

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.

Selective oxidation of cyclohexane with hydrogen peroxide in the presence of copper pyrophosphate

Liquid phase oxidation of cyclohexane was carried out under mild reaction condition over copper pyrophosphate catalyst in CH3CN using hydrogen peroxide as an oxidant at the temperature between 25 and 80 degrees C. The copper pyrophosphate catalyst was characterized by means of XRD, FT-IR and water contact angle measurement. It was found that appropriate surface hydrophobicity is the key factor for the excellent performance of the catalyst. In addition, a significant improvement for the cyclohexane conversion in the presence of organic acid was observed.

Harvesting Excitons Via Two Parallel Channels for Efficient White Organic LEDs with Nearly 100% Internal Quantum Efficiency: Fabrication and Emission-Mechanism Analysis

By incorporating two phosphorescent dyes, namely, iridium(III)[bis(4,6-difluorophenyl)-pyridinato-N,C-2']picolinate (Flrpic) for blue emission and bis(2-(9,9-diethyl-9H-fluoren-2-yl)-1-phenyl-1 H-benzoimidazol-N,C-3) iridium(acetylacetonate) ((fbi)(2)Ir(acac)) for orange emission, into a single-energy well-like emissive layer, an extremely high-efficiency white organic light-emitting diode (WOLED) with excellent color stability is demonstrated. This device can achieve a peak forward-viewing power efficiency of 42.5 lm W-1, corresponding to an external quantum efficiency (EQE) of 19.3% and a current efficiency of 52.8 cd A(-1). Systematic studies of the dopants, host and dopant-doped host films in terms of photophysical properties (including absorption, photoluminescence, and excitation spectra), transient photoluminescence, current density-voltage characteristics, and temperature-dependent electroluminescence spectra are subsequently performed, from which it is concluded that the emission natures of Flrpic and (fbi)(2)Ir(acac) are, respectively, host-guest energy transfer and a direct exciton formation process. These two parallel pathways serve to channel the overall excitons to both dopants, greatly reducing unfavorable energy losses.

Solution-processible multi-component cyclometalated iridium phosphors for high-efficiency orange-emitting OLEDs and their potential use as white light sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole-transporting carbazole and fluorene-based 2-phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the pi-conjugation through incorporation of electron- pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest oc- cupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium-based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo- and electroluminescence properties of these phosphorescent carbazolylfluorene-functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light-emitting diodes (OLEDs) using these complexes as the solution-processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole-transporting layer.I These orange-emitting devices can produce a maximum current efficiency of similar to 30 cd A(-1) corresponding to an external quantum efficiency of similar to 10 % ph/el (photons per electron) and a power efficiency of similar to 14 Im W-1.

Synthesis, crystal structure, and magnetic properties of {[Cu(oxbe)]Mn(H2O)[Cu(oxbe)(DMF)]}(n)center dot nDMF center dot nH(2)O: From dissymmetrical mononuclear entities to a 3D heterometallic supramolecular coordination polymer

Self-assembly of the building block [Cu(oxbe)](-) with Mn(II) led to a novel coordination polymer {[Cu(oxbe)]Mn(H2O)(Cu(oxbe)(DMF)]}(n).nDMF.nH(2)O, where H(3)oxbe is a new dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)-oxamido and DMF = dimethylformamide. The crystal forms in the triclinic system, space group P(1)over-bar, with a = 9.260(4) angstorm, b = 12.833(5) angstrom, c = 15.274(6) angstrom , alpha = 76.18(3)degrees, beta = 82.7(3)degrees, gamma = 82.31(3)degrees, and Z = 2. The crystal structure of the title complex reveals that the two-dimensional bimetallic layers are constructed of (CuMnII)-Mn-II-Cu-II chains linked together by carboxylate bridge and hydrogen bonds help to produce a novel three-dimensional channel-like structure. The magnetic susceptibility measurements (5-300 K) were analyzed by means of the Hamiltonian (H)over-cap = -2J(S)over-cap (Mn)((S)over-cap(Cu1) + (S)over-cap(Cu2)), leading to J = -17.4 cm(-1).

From dissymmetrical mononuclear entities to centrosymmetrical heterotrinuclear complex with 2D supramolecular structure: synthesis, characterization, crystal structure, and magnetic properties

A new centrosymmetrical heterotrinuclear complex, {[Cu(oxbe)](2)Co(H2O)(2)}.2DMF.DMA with 2D supramolecular structure, has been obtained by the self-assembly of a dissymmetrical building block [Cu(oxbe)](-) with bivalent metal ion Co2+, where H(3)oxbe is dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)oxamido, DMF = dimethylformamide, DMA = dimethylamine. Its structure was determined by single crystal X-ray analysis. The molecular structure is centrosymmetrical with the cobalt atom lying on an inversion center. Through the hydrogen bonds and d-pi stacking interactions, a 2D supramolecular structure is formed. This study exemplifies a new method for the assembly of supramolecular structure using a dissymmetrical brick. Magnetic susceptibility measurements (5-300 K) indicate that the central cobalt and terminal copper metal ions are antiferromagnetically coupled with J = -23.1 cm(-1).

Ethylene polymerization by self-immobilized neutral nickel catalysts bearing allyl groups

[Ni(Ph)(PPh3)(N,O)] complexes containing phenyliminophenolato ligands (N,O) (1: N,O = A; 2: N,O = B; 3: N,O = Q 4: N,O = D; 5: N,O = E) have been synthesized and characterized. The molecular structure of 4 was determined by single-crystal X-ray analysis. Complexes 2-5 bearing allyl groups have been investigated as self-immobilized catalysts for ethylene polymerization without the use of co-catalysts. The high ethylene polymerization activities of ca. 10(5) g.PE mol(-1) Ni.h(-1) and high molecular weight (M-w approximate to 10(5)) of polyethylene could be accomplished by changing the ligand structures and reaction conditions. The self-immobilization of catalysts brings about a dramatic increase in the catalytic activities of ethylene polymerization.

Synthesis and characterization of two novel [Ru(bpy)(2)(phen)](2+)-based electrochemiluminescent labels

Two novel electrochemiluminescent labels, bis(2,2'-bipyridine)[5-(3-carboxylic acid-propionamido)1,10-phenanthroline]ruthenium(II) hexafluorophosphate dihydrate and bis(2,2'-bipyridine)[5-(4-carboxylic acid-butanamido)-1,10-phenanthroline]ruthenium(II) hexafluorophosphate dihydrate, were synthesized and confirmed by IRelemental analysis, and H-1-NMR spectra were completely assigned using the (HH)-H-1-H-1 COSY technique. Cyclic voltammograms with different scan rates showed quasireversible electrochemical behaviour of the two Ru (II) complex labels in MeCN solution. Electronic absorption, photoluminescence and electrochemiluminescence of Ru(II) complexes were also characterized. Copyright (C) 2000 John Wiley & Sons, Ltd.

Two dimensional nuclear magnetic resonance analysis of ruthenium-(4,4'-dimethyl-2,2'-bipyridine)(2) (2,2'-bipyridine-4,4'-dicarboxylic acid) (PF6)(2)

The (1) H and C-13 NMR spectra are reported for Ru(4, 4'-dimethyl-2,2'-bipyridene)(2) (2,2'-bipyridine-4,4'-dicarboxylic acid) (PF6)(2) that can be used as a new electrochemiluminescent probe in immunoasssay and nucleic acid hybridization assay. Because of the effect ol:Ru atom ligands and complex steric configuration, it is difficult to attribute spectra of the title molecular, By using 2D (1) H-(1) H COSY and (1) H-C-13 HETCOR method, the proton and C-13 NMR spectra are assigned completely, which provides a satisfactory method to quantitative and qualitative, analysis of the title moleculer in the further study.

Synthesis, electrochemistry, and fluorescence of two Ru(phen)(3)(2+)-based surfactants

Two new Ru(phen)(3)(2+)-based surfactants, Ru(phen)(2)(phenNHCO-C-11)(PF6)(2) and Ru(phen)(2)(phenNHCO-C-17)(PF6)(2), have been designed and synthesized, whose chemical structures were characterized by means of IR, H-1 NMR and MS. Also, electrochemistry and fluorescence of them are reported.

Synthesis, electrochemistry, fluorescence and ECL of Ru (phen)(2) (dcbpy) (PF6)(2)

A new ECL-active species, Ru (phen)(2) (dcbpy) (PF6)(2), has been designed and synthesized. Its structure was confirmed by means of IR, ESI-MS and 2D NMR. Also, its properties of electrochemistry, fluorescence and ECL are reported, which have suggested a good hope of being used in electrochemiluminescent immunoassay and nucleic acid hybridization.