Chiral synthesis on catalysts immobilized in microporous and mesoporous materials

This paper reviews the recent progress made in the asymmetric synthesis on chiral catalysts in porous materials and discusses the effects of surface and pores on enantio-selectivity (confinement effect). This paper also summarizes various approaches of immobilization of the chiral catalysts onto surfaces and into pores of solid inorganic supports such as microporous and mesoporous materials. The most important reactions surveyed for the chiral synthesis in porous materials include epoxidation. hydrogenation, hydroformylation, Aldol and Diels-Alder reactions, etc. The confinement effect originated from the surfaces and the pores turns out to be a general phenomenon. which may make the enantioselectivity increase (positive effect) or decrease (negative effect). The confinement effect becomes more pronounced particularly when the bonding between the catalyst and the surface is more rigid and the pore size is tuned to a suitable range. It is proposed that the confinement in chiral synthesis is essentially a consequence of subtle change in transition states induced by weak-interaction in pores or on surfaces. It is also anticipated that the enantioselectivity could be improved by tuning the confinement effect based on the molecular designing of the pore/surface and the immobilized catalysts according to the requirements of chiral reactions.

The synthesis of nanostructured W2C on ultrahigh surface area carbon materials via carbothermal hydrogen reduction

Nanostructured tungsten carbides were synthesized, for the first time, with a size distribution of 5-12 nm on ultrahigh surface area carbon material, by carbothermal hydrogen reduction (CHR) at 850degreesC and metal Ni promoted CHR at 650 degreesC.

Preparation and characteristics of nonflammable polyimide materials

The thermal and flame-retardant properties of homo- and copolyimides were evaluated. Those containing sulfone linkages in the backbone were found to be more flame retardant. Both properties were dependent on the composition. A polyimide/silica nanocomposite was obtained through sol-gel processing. The effects of the addition of silica an the dispersion, interfacial adhesion, fire resistance, mechanical properties, and thermal stability of the composites were investigated. SEM analysis showed a good dispersion of silica with a diameter of 50-300 nm in the organic matrices. The addition of silica increased the fire retardancy and mechanical properties of the composites. (C) 2000 John Wiley & Sons, Inc.

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.

Red-light-emitting iridium complexes with hole-transporting 9-arylcarbazole moieties for electrophosphorescence efficiency/color purity trade-off optimizationE

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations

Efficient red organic light-emitting diode sensitized by phosphorescent Ir compound

The efficiencies of red organic light-emitting diode (OLED) using tris-(8-hydroxy-quinoline)aluminum (Alq(3)) as host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant were greatly increased by adding a small amount (0.3 wt%) of Ir compound, iridium(III) bis(3-(2-benzothiazolyl)-7-(diethylamino)-2H-1-benzopyran-2-onato-N-',C-4) (acetyl acetonate) (Ir(C6)(2)(acac)), as a sensitizer

Red-Light-Emitting Iridium Complexes with Hole-Transporting 9-Arylcarbazole Moieties for Electrophosphorescence Efficiency/ Color Purity Trade-off Optimization

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations. The highest occupied molecular orbital levels of these complexes are raised by the integration of a carbazole unit to the iridium isoquinoline core so that the hole-transporting ability is improved in the resulting complexes relative to those with I-phenylisoquinoline ligands. All of the complexes are highly thermally stable and emit an intense red light at room temperature with relatively short lifetimes that are beneficial for highly efficient organic light-emitting diodes (OLEDs).

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.

Cross-linkable aromatic amines as materials for insoluble hole-transporting layers in light-emitting devices

A series of cross-linkable aromatic amines has been synthesized by the multi-step synthetic rout. Full characterization of their structure by H-1 NMR-, IR- and mass spectrometry is presented. The synthesized materials were examined by various techniques including differential scanning calorimetry, thermogravimetry, UV and electron photoemission spectrometry.

One-step preparation of hybrid materials of polyacrylamide networks and gold nanoparticles

Hybrid materials of polyacrylamide networks and gold nanoparticles were prepared by directly heating an aqueous solution containing HAuCl4, acrylamide, N,N'-methylenebisacrylamide, and sodium sulfite (Na2SO3). Acrylamide, N,N'-methylenebisacrylamide, and Na2SO3 were used as monomers, crosslinking agent, and initiator, respectively.

Design and synthesis of near-IR luminescent mesoporous materials covalently linked with tris(8-hydroxyquinolinate) lanthanide(III) complexes

By using the bifunctional ligand, 8-hydroxyquinoline-functionalized organosilane (Q-Si), the new mesoporous material Q-MCM-41 covalently bonded with 8-hydroxyquinoline was synthesized. Through the ligand exchange reaction, the new near-infrared (NIR) luminescent mesoporous LnQ(3)-MCM-41 (Ln = Er, Nd, Yb) materials were prepared by linking the lanthanide quinolinate complexes to the ordered mesoporous Q-MCM-41 material. The LnQ(3)-MCM-41 materials were characterized by powder X-ray diffraction and N-2 adsorption/desorption, and they all show the characteristic mesoporous structure of MCM-41 with highly uniform pore size distributions.

Ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complex-functionalized mesoporous SBA-15 materials that emit in the near-infrared range

The tertiary lanthanide complexes [Ln(hfth)(3)phen] (Ln=Er, Nd, Yb, Sm) and [Pr(tfnb)(3)phen] have been Successfully covalently attached in the ordered SBA-15 mesoporous materials via a functionalized 1,10-phenanthroline group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (Phen-Si). The derivative materials [denoted as Ln(hfth)(3)phen-S15 and Pr(tfnb)(3)phen-S15; Ln=Er, Yb, Nd, Sm; hfth=4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb=4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate] were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and N-2 adsorption/desorption.