Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached.

Synthesis and characterization of novel neutral nickel complexes bearing fluorinated salicylaidiminato ligands and their catalytic behavior for vinylic polymerization of norbornene

A series of salicylaldimine-based neutral Ni(II) complexes (3a-j) [ArN = CH(C6H40)]Ni(PPh3)Ph [3a,Ar = C6H5; 3b,Ar = C6H4F(o); 3c, Ar = C6H4F(m); 3d, Ar = C6H4F(p); 3e, Ar = C6H3F2(2,4); 3f, Ar = C6H3F2(2,5); 3g, Ar = C6H3F2(2,6); 3h, Ar = C6H3F2(3,5); 3i, Ar = C6H2F3(3,4,5); 3j, Ar = C6H5] have been synthesized in good yield, and the structures of complexes 3a and 3i have been confirmed by X-ray crystallographic analysis. Using modified methylaluminoxane as a cocatalyst, these neutral Ni(II) complexes exhibited high catalytic activities for the vinylic polymerization of norbornene.

Fixation of carbon dioxide into aliphatic polycarbonate, cobalt porphyrin catalyzed regio-specific poly(propylene carbonate) with high molecular weight

Cobalt porphyrin complex ((TPPCoX)-X-III) (TPP = 5, 10, 15, 20-Tetraphenylporphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio-specific copolymerization of propylene oxide and carbon dioxide. A turnover frequency of 188 h(-1) was achieved after 5 h, and the byproduct propylene carbonate was successfully controlled to below 1%, where the obtained poly(propylene carbonate) (PPC) showed number average molecular weight (M-n) of 48 kg/mol, head-to-tail content of 93%, and carbonate linkage of over 99%.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Red-Emitting Polyfluorenes Grafted with Quinoline-Based Iridium Complex: "Simple Polymeric Chain, Unexpected High Efficiency"

A series of red-light emitting electrophosphorescent polyfluorenes (PFs) with varying content of a quinoline-based iridium complex, (PPQ)(2)Ir(acac) (bis(2,4-diphenylquinolyl-N,C-2') iridium(acetylacetonate)), in the side chain are synthesized by Suzuki polycondensation. Because of the efficient Forster energy transfer from the PF main chain to (PPQ)(2)Ir(acac) and direct charge trapping on the complex, the electroluminescent emission from PF is nearly completely quenched, even though the amount of iridium complex I incorporated into the polymers is as low as 1 mol %. Based on a single-layer device configuration, a luminous efficiency of up to 5.0 cd A(-1) with a luminance of 2000 cd m(-2) and Commission Internationale de L'Eclairage coordinates of (0.63, 0.35) (x, y) is realized, which is far superior to that of previously reported red-light emitting PFs containing benzothiazole- and isoquinoline-based iridium complexes.

Synthesis, characterization and electrophosphorescent properties of mononuclear platinum(II) complexes based on 2-phenylbenzoimidazole derivatives

The rational design, synthesis and characterization of five phosphorescent platinum complexes [(C boolean AND N) Pt(acac)] [Hacac = acetylacetone, HC boolean AND N = 1-methyl-2-(4-fluorophenyl)benzoimidazole (H-FMBI), 1-methyl-2-phenylbenzoimidazole (H-MBI), 1,2-diphenyl-benzoimidazole (H-PBI), 1-(4-(3,6-di-t-butylcarbazol-9-yl)) phenyl-2-phenylbenzoimidazole (t-BuCz-H-PBI), and 1-(4-(3,6-di-(3,6-di-t-butyl-carbazol-9-yl))carbazol-9-yl) phenyl-2-phenylbenzoimidazole (t-BuCzCz-H-PBI)] have been discussed. The crystal structure of (MBI) Pt(acac) shows a nearly ideal square planar geometry around Pt atom and the weak intermolecular interactions with pi-pi spacing of 3.55 angstrom. All of the complexes emit green phosphorescence from the metal-to-ligand charge-transfer (MLCT) excited state with high quantum efficiency (0.08-0.17) at room temperature.

Novel luminescent iminephosphine complex of copper(I) with high photochemical and electrochemical stability

Luminescent heteroleptic Cu-I complexes based on asymmetrical iminephosphine ligands exhibit improved electrochemical and photochemical stability as compared to the analogous complexes based on traditional diimine or diphosphine ligands.

The synthesis and properties of meso-tetra(4-alkylamidophenyl)porphyrin liquid crystals and their Zn complexes

A series of novel, long-chain-substituted, porphyrin derivatives, meso-tetra (4-alkylamidophenyl) porphyrin ligands and their Zn complexes (alkyl = 8,10,12,14,16,18) were prepared by acylation of the amino groups of 5,10,15,20-tetra(4-aminophenyl)porphyrin by alkyl chloride. Mesomorphism was investigated by DSC, polarized optical microscopy (POM) and X-ray diffraction (XRD). Only ligands containing chains > 12 carbon atoms displayed liquid crystalline behaviour, which exhibited a high phase transition temperature and a broad mesophase temperature span, Zn complexes showed no liquid crystalline behaviour. Cyclic voltammetry, luminescence spectra and surface photovoltage spectroscopy revealed that covalent linking of an alkylamido group to the tetraphenylporphyrin molecule influences, significantly, the properties of the porphyrin macrocycle.

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

A series of cyclometalating platinum(II) complexes with substituted 9-arylcarbazolyl chromophores have been synthesized and characterized. These complexes are thermally stable and most of them have been characterized by X-ray crystallography. The phosphorescence emissions of the complexes are dominated by (MLCT)-M-3 excited states. The excited state properties of these complexes can be modulated by varying the electronic characteristics of the cyclometalating ligands via substituent effects, thus allowing the emission to be tuned from bright green to yellow, orange and red light. The correlation between the functional properties of these metallophosphors and the results of density functional theory calculations was made. Because of the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such moiety can increase the highest occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent platinum(II) phosphor with 2-phenylpyridine ligand.

Copolymerization of ethylene with norbornene catalyzed by cationic rare earth metal fluorenyl functionalized N-heterocyclic carbene complexes

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH2SiMe3)(2) (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH2SiMe3)(2) ((tBu)Flu-NHC = 2,7-(Bu2C13H6CH2CH2)-Bu-t(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified N-heterocyclic carbene (Ind-NHC)Ln(CH2SiMe3)(2) (Ind-NHC = C9H6CH2CH2(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (3a); Lu (3d)), under the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)(4)], showed varied catalytic activities toward homo- and copolymerization of ethylene and norbornene. Among which the scandium complexes, in spite of ligand type, exhibited medium to high catalytic activity for ethylene polymerization (10(5) g mol(Sc)(-1) h(-1) atm(-1)), but all were almost inert to norbornene polymerization. Remarkably, higher activity was found for the copolymerization of ethylene and norbornene when using Sc based catalytic systems, which reached up to 5 x 10(6) g mol(Sc)(-1) h(-1) atm(-1) with 2a. The composition of the isolated copolymer was varying from random to alternating according to the feed ratio of the two monomers (r(E) = 4.1, r(NB) = 0.013).

Conjugation of Selenophene with Bipyridine for a High Molar Extinction Coefficient Sensitizer in Dye-Sensitized Solar Cells

A high molar extinction coefficient heteroleptic polypyridyl ruthenium sensitizer, featuring a conjugated electron-rich selenophene unit in its ancillary ligand, has been synthesized and demonstrated as an efficient sensitizer in dye-sensitized solar cells. A nanocrystalline titania film stained with this sensitizer shows improved optical absorptivity, which is highly desirable for dye-sensitized solar cells with a thin photoactive layer. With preliminary testing, this sensitizer has already achieved a high efficiency of 10.6% measured under the air mass 1.5 global conditions.

Dye-Sensitized Solar Cells with a High Absorptivity Ruthenium Sensitizer Featuring a 2-(Hexylthio)thiophene Conjugated Bipyridine

We conjugated 2-(hexylthio)thiophene with bipyridine to construct a new heteroleptic polypyridyl ruthenium sensitizer exhibiting a charge-transfer band at 550 nm with a molar extinction coefficient of 18.7 x 10(3) M-1 cm(-1). In contrast to its analogues Z907 and C101, a mesoporous titania film stained with this new sensitizer featured a short light absorption length, allowing for the use of a thin photoactive layer for efficient light-harvesting and conversion of solar energy to electricity. With a preliminary testing, we have reached 11.4% overall power conversion efficiency measured at the air mass 1.5 global conditions. Transient photoelectrical decays and electrical impedance spectra were analyzed to picture the intrinsic physics of temperature-dependent photovoltage and photocurrent.

An Extremely High Molar Extinction Coefficient Ruthenium Sensitizer in Dye-Sensitized Solar Cells: The Effects of pi-Conjugation Extension

We report a heteroleptic ruthenium complex (007) featuring the electron-rich 5-octyl-2,2'-bis(3,4-ethylenedioxythiophene) moiety conjugated with 2,2-bipyridine and exhibiting 10.7% power conversion efficiency measured at the AM1.5G conditions, thanks to the enhanced light-harvesting that is closely related to photocurrent. This C107 sensitizer has an extremely high molar extinction coefficient,of 27.4 x 10(3) M-1 cm(-1) at 559 nm in comparison to its analogue C103 (20.5 x 10(3) M-1 cm(-1) at 550 nm) or Z907 (12.2 x 10(3) M(-1)cm(-1) at 521 nm) with the corresponding 5-hexyl-3,4-ethylenedioxythiopliene- or nonyl-substituted bipyridyl unit. The augmentation of molar extinction coefficients and the bathochromic shift of low-energy absorption peaks along with the pi-conjugation extension are detailed by TD-DFT calculations. The absorptivity of mesoporous titania films grafted with Z907, C103, or C107 sublinearly increases with the molar extinction coefficient of sensitizers, which is consistent with the finding derived from the surface coverage measurements that the packing density of those sensitizers decreases with the geometric enlargement of ancillary ligands.

Facile, Efficient Copolymerization of Ethylene with Bicyclic, Non-Conjugated Dienes by Titanium Complexes Bearing Bis(beta-Enaminoketonato) Ligands

Copolymerizations of ethylene with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene under the action of various titanium complexes bearing bis(beta-enaminoketonato) chelate ligands of the type, [(RN)-N-1=C(R-2)CH=C(R-3)O](2)TiCl2 (1, R-1=Ph, R-2=CF3, R-3=Ph; 2, R-1=C6H4F-p, R-2=CF3, R-3=Ph; 3, R-1=Ph, R-2=CF3, R-3=t-Bu; 4, R-1=C6H4F-p, R-2=CF3, R-3=t-Bu; 5, R-1=Ph, R-2=CH3, R-3=CF3; 6, R-1=C6H4F-p, R-2=CH3 R-3=CF3), have been shown to occur with the regioselective insertion of the endocyclic double bond of the monomer into the copolymer chain, leaving the exocyclic vinyl double bond as a pendant unsaturation. The ligand modification strongly affects the copolymerization behaviour. High catalytic activities and efficient co-monomer incorporation can be easily obtained by optimizing the catalyst structures and polymerization conditions.

Synthesis, Structural Characterization, and Olefin Polymerization Behavior of Vanadium(III) Complexes Bearing Tridentate Schiff Base Ligands

Vanadium(III) complexes bearing tridentate salicylaldiminato ligands (2a-f) [OC6H4CH=NL]VCl2(THF) (L = CH2CH2OMe, 2a; CH2CH2NMe2, 2b; CH2C5H4N, 2c; 8-C9H6N (quinoline), 2d; 2-MeSC6H4, 2e; 2-Ph2PC6H4, 2f) and tridentate beta-enaminoketonato ligands [OC6H8CH=N-2-Ph2PC6H4]VCl2(THF) (2g) and [O(Ph)C=CHCH=N-2-Ph2PC6H4]VCl2(THF) (2h) were prepared from VCl3(THF)(3) by treating with 1.0 equiv of the deprotonated ligands in tetrahydrofuran (THF). These complexes were characterized by FTIR and mass spectrometry as well as elemental analysis. Structures of complexes 2e, 2f, and 2h were further confirmed by X-ray crystallographic analysis. These complexes were investigated as catalysts for olefin polymerization in the presence of organoaluminum compounds. On activation with Et2AlCl, complexes 2a-h exhibited high catalytic activities toward ethylene polymerization (up to 20.64 kg PE/mmol(v) center dot h center dot bar) even at high temperature, suggesting these catalysts possess high thermal stability.