DFT/TDDFT Studies on the Electronic Structures and Spectral Properties of Rhenium(I) Pyridinybenzoimidazole Complexes

The electronic structures and spectral properties of three Re(I) complexes [Re(CO)(3)XL] (X = Br, Cl; L = 1-(4-5 '-phenyl-1.3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), and 2-(1-ethyl benzimidazol-2-yl)pyridi ne (3)) were investigated theoretically. The ground and the lowest lying triplet excited states were full optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. TDDFT/PCM calculations have been employed to predict the absorption and emission spectra starting from the ground and excited state geometries, respectively.

Syntheses, structures and luminescence of silver(I) sulfonate complexes with PPh3 ligand

In this paper, four new luminescent silver(I) sulfonate complexes with PPh3, namely Ag(L1)(PPh3)(2) (1), Ag(L2)(PPh3)(3) (2), [Ag-2(L3)(PPh3)(4) (H2O)center dot 1.5CH(3)CN center dot 0.5H(2)O (3) and [Ag-4(L4)(PPh3)(10)]center dot 8H(2)O (4), where L1=p-toluenesulfonate, L2=1-naphthalenesulfonate, L3=3-carboxylate-4-hydroxybenzenesulfonate, L4=1, 3, 6, 8-pyrenetetrasulfonatc and PPh3=triphenylphosphine, have been synthesized and characterized. The crystal structures were determined by single-crystal X-ray diffraction method. Compounds 1, 2, 3 and 4 adopt discrete structures rather than polymeric structures. Compounds I and 2 show mononuclear structures while 3 and 4 are dinuclear and tetranuclear molecules, respectively. Moreover the numbers of PPh3 molecules coordinating to one silver center are two or three. The photoluminescent properties of 1, 2 and 3 are discussed.

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.

Theoretical studies on electronic structures, spectra and charge transporting properties of a series of Pt((CN)-N-Lambda)(2) complexes

We report a quantum-chemical study of electronic, optical and charge transporting properties of four platinum (II) complexes, pt((CN)-N-Lambda)(2) ((CN)-N-Lambda=phenylpyridine or thiophenepyridine). The lowest-lying absorptions at 442, 440, 447 and 429 nm are all attributed to the mixed transition characters of metal-to-ligand charge transfer (MLCT) and ligand-centered (LC) pi - pi(*) transition. While, unexpectedly, the lowest-lying phosphorescent emissions at 663, 660, 675 and 742 nm are mainly from metal-to-ligand charge transfer ((MLCT)-M-3) ligand-centered (LC) pi ->pi* transition. Ionization potential (IP), electron affinities (EA) and reorganization energy P (lambda(hole/electron)) were obtained to evaluate the charge transfer and balance properties between hole and electron.

Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to Alkynes

The B3LYP hybrid density functional method has been carried Out to Study theoretically the mechanisin of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH3)(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH3)2, and in path C of each reaction, the first step is the PH3 dissociation front Pd(PH3)2 to form monophosphine complex Pd(PH3) For both reactions, path B is favored.

Theoretical Studies on the Reaction Mechanism of Platinum-Catalyzed Diboration of Allenes

The reaction mechanism of Pt(0)-catalyzed diboration reaction of allenes is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. The electronic mechanisms of the allene insertion into the Pt-B bond are discussed in terms of the electron donation, back-donation, and d-pi interaction. During allene insertion into the Pt-B bond, the internal carbon atom of allene is preferred over the terminal one due to the stronger electron back-donation and stronger charge transfer in the former case than that in the latter one.

Reaction Mechanism of Palladium-Catalyzed Silastannation of Allenes by Density Functional Theory

The reaction mechanism of Pd(O)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed ill terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.

Efficient Electrophosphorescence from a Platinum Metallopolyyne Featuring a 2,7-Carbazole Chromophore

The synthesis, thermal and emission properties of an electrophosphorescent platinum(II) metallopolyyne polymer consisting of 9-butylcarbazole-2,7-diyl spacer P1 are described. The optical and electronic properties of P1 are compared to their molecular diplatinum(II) and digold(I) model complexes. The photophysical properties of P1 are somehow analogous to its 2,7-fluorene-linked congener but differs significantly from that for the 3,6-carbazole derivative. Its optical band gap is notably reduced as compared to that for the 3,6-carbazole analog. Multi-layer polymer light-emitting diodes (PLEDs) were fabricated with P1 as the emitting layer which gave a strong green-yellow electrophosphorescence. The best PLED can reach the maximum current efficiency of 4.7 cd . A(-1) at 5 wt.-% doping level, corresponding to an external quantum efficiency of 1.5%. This represents the first literature example of efficient PLEDs exhibiting pure triplet emission under electrical excitation for metallopolyynes without the concomitant singlet emission.

Phenylthiolate as a sigma- and pi-donor ligand: synthesis of a 3-D organometallic coordination polymer [K2Fe(SPh)(4)](n)

The synthesis and crystal structure of the first mixed-metal organometallic polymer network containing phenylthiolato ligands, [K2Fe(SPh)(4)](n), are investigated. The simple phenyl-thiolate acts as a sigma- and pi-donor ligand to give a 3-D potassium iron coordination polymer with both metal-carbon and metal-sulfur coordination interactions.

STUDIED ON THE SIMULTANEOUS SPECTROPHOTOMETRIC DETERMINATION OF INORGANIC MULTICOMPONENT SYSTEMS .3. DETERMINATION OF MICROAMOUNTS OF TUNGSTEN, MOLYBDENUM AND TITANIUM

The absorption spectra of W, Mo and Ti-phenylfluorone cetyltrimethylammonium bromide complexes and the optimum conditions for the simultaneous spectrophotometric determination of microamounts of W, Mo and Ti were studied. In order to examine the effect of the errors of calibration matrix on the analytical resulte, the approach of selecting the analytical wavelengths was investigated and the comparison of computation results between AKC method (the matrix representation of Beer-Lambert's Law) and ...

Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing beta-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L-1)PPh3 (1), Cu(L-2)(PPh3)(2) (2) ([L-1](-) = [{N((C6H3Pr2)-Pr-i-2,6)C(H)}(2)CPh](-); [L-2](-) = [{N(C6H5)C(H)}(2)CPh](-)) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered beta-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.

Novel heteroleptic Cu-I complexes with tunable emission color for efficient phosphorescent light-emitting diodes

A series of orange-red to red phosphorescent heteroleptic Cu-I complexes (the first ligand: 2,2 '-biquinoline (bq), 4,4 '-diphenyl2,2 '-biquinoline (dpbq) or 3,3 '-methylen-4,4 '-diphenyl-2,2 '-biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2-(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline-type ligands, complexes [Cu(mdpbq)(PPh3)(2)](BF4) and [Cu(mdpbq)(DPEphos)](BF4) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N-(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), phosphorescent organic light-emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF4) exhibits the best device performance. With the device structure of ITO/PEDOT/ TCCz:[Cu(mdpbq)(DPEphos)](BF4) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A(-1) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu complexes with red emission.

Highly efficient green phosphorescent organic light-emitting diodes based on Cu-I complexes

Mononuclear Cu-I complexes with mixed ligands are used to fabricate green phosphorescent organic light-emitting diodes. The electroluminescence (EL) maximum at 524 nm coincides well with its photoluminescent (PL) spectrum in poly(methyl methacrylate) film (see Figure). A maximum current efficiency of 10.5 cd A(-1) at 105 cd m(-2) and a maximum brightness up to 1663 cd m(-2) are