New synthesis of highly potential efficient bluish‐green electroluminescent materials based on 1,3,4‐oxadiazole–triazolopyridinone–carbazole derivatives for single‐layer devices

New potential bluish‐green electroluminescent materials of 1,3,4‐oxadiazole–triazolopyridin‐ one–carbazole derivatives were synthesized and characterized for single‐layer devices. Carbazole, pyridine, and triazolopyridinone were completely introduced into 1,3,4‐oxadiazole skeletal to play assistant roles in controlling fundamental photolytic process due to the electron‐donating nature, excellent photoconductivity, and flexible structure properties. Following the spectroscopic studies and the measurements of cyclic voltammogram, 1,3,4‐oxadiazole–triazolopyridinone–carbazole derivatives were highly efficient bluish‐green electroluminescent materials. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:160–165, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20201     

Hydrogen‐bonded supramolecular networks of N,N′‐bis(4‐pyridylmethyl)oxalamide and 4,4′‐{[oxalylbis(azanediyl)]dimethylene}dipyridinium dinitrate

The molecule of N,N′‐bis(4‐pyridylmethyl)oxalamide, C₁₄H₁₄N₄O₂, (I) or 4py‐ox, has an inversion center in the middle of the oxalamide group. Adjacent molecules are then linked through intermolecular N—H...N and C—H...O hydrogen bonds, forming an extended supramolecular network. 4,4′‐{[Oxalylbis(azanediyl)]dimethylene}dipyridinium dinitrate, C₁₄H₁₆N₄O₂²⁺·2NO₃⁻, (II), contains a diprotonated 4py‐ox cation and two nitrate counter‐anions. Each nitrate ion is hydrogen bonded to four 4py‐ox cations via intermolecular N—H...O and C—H...O interactions. Adjacent 4py‐ox cations are linked through weak C—H...O hydrogen bonding between an α‐pyridinium C atom and an oxalamide O atom, forming a two‐dimensional extended supramolecular network.     

Anion‐ and Solvent‐Induced Assembly and Reversible Structural Transformation of d10‐Metal Coordination Architectures Containing N‐(4‐(4‐Aminophenyloxy)phenyl)isonicotinamide

We set out studies on anion‐ and solvent‐induced assembly based on the ligand N‐(4‐(4‐aminophenyloxy)phenyl)isonicotinamide (papoa), which is synthesized to show a bent and flexible backbone. Reactions of papoa with ZnX₂ (X=Cl, Br, and I) gave the dinuclear macrocycles ([ZnX₂(papoa)]₂; X=Cl ( 1 a ), Br ( 2 a ), I ( 3 )), the structure of which was determined by X‐ray diffraction. Notably, the less bulky Cl and Br compounds afforded the coordinated imine in acetone (i.e., [ZnX₂(papoi)]₂, papoi=N‐(4‐(4‐(propan‐2‐ylideneamino)phenoxy)phenyl)isonicotinamide; X=Cl ( 1 b ), Br ( 2 b )), whereas the iodine one only gave the coordinated amine compound 3 under the same reaction condition. In fact, the coordinated imine can return to the amine analogue upon exposure to air or in DMSO, which has been monitored by ¹H NMR spectroscopy and powder X‐ray diffraction. Both the dinuclear [Zn(papoa)(NO₃)₂]₂ ( 4 a ) and the 1D [Zn(papoa)₂(NO₃)₂]_n ( 4 b ) were formed from the reaction of Zn(NO₃)₂ and papoa in mixed solvents with acetone and acetonitrile, respectively. In addition, Cd(ClO₄)₂ can react with papoa to give the 1D framework {[Cd(papoa)₂(CH₃CN)₂](ClO₄)₂}_n ( 5 a ) and the 2D framework [Cd(papoa)₂(ClO₄)₂]_n ( 5 b ), depending on the solvent used, that is, MeOH and CH₃CN, respectively. Importantly, the 1D framework with axially coordinated CH₃CN molecules and the 2D framework with axially coordinated ClO₄^? ions can be interconverted by heating and grinding in the presence of CH₃CN, respectively. Such a reversible structural transformation process was proven by PXRD studies.     

Magnetic field dependence of JC in SNS junctions

Critical currents for triple layer superconducting-normal metal-superconducting (SNS) junctions have been measured with the normal metal in the thick-clean limit in order to determine the spatial variation of the order paremeter as a function of magnetic field (H). Critical currents fall exponentially with H as might be expected if the decay length, K^-1_N, varies linearly with H. The diffusivity, D_N, derived from the measured depairing parameter, α=D_NeH/c, agrees with the diffusivity determined from resistivity measurements.     

PtII Complexes with 6‐(5‐Trifluoromethyl‐Pyrazol‐3‐yl)‐2,2′‐Bipyridine Terdentate Chelating Ligands: Synthesis,Characterization, and Luminescent Properties

A series of Pt^II complexes Pt(fpbpy)Cl ( 1 ), Pt(fpbpy)(OAc) ( 2 ), Pt(fpbpy)(NHCOMe) ( 3 ), Pt(fpbpy)(NHCOEt) ( 4 ), and [Pt(fpbpy)(NCMe)](BF₄) ( 5 ) with deprotonated 6‐(5‐trifluoromethyl‐pyrazol‐3‐yl)‐2,2′‐bipyridine terdentate ligand are prepared, among which 1 is converted to complexes 2 – 5 by a simple ligand substitution. Alternatively, acetamide complex 3 is prepared by hydrolysis of acetonitrile complex 5 , while the back conversion from 3 to 1 is regulated by the addition of HCl solution, showing the reaction sequence 1 → 5 → 3 → 1 . Multilayer OLED devices are successfully fabricated by using triphenyl‐(4‐(9‐phenyl‐9H‐fluoren‐9‐yl)phenyl) silane (TPSi‐F) as host material and with doping concentrations of 1 varying from 7 to 100 %. The electroluminescence showed a substantial red‐shifting versus the normal photoluminescence detected in solution. Moreover, at a doping concentration of 28 %, the device showed a saturated red luminescence with a maximum external quantum yield of 8.5 % at 20 mA cm^?2 and a peak luminescence of 47 543 cd m^?2 at 18.5 V.     

Enhanced Performance of Solution‐Processed TESPE‐ADT Thin‐Film Transistors

A solution‐processed anthradithiophene derivative, 5,11‐bis(4‐triethylsilylphenylethynyl)anthradithiophene (TESPE‐ADT), is studied for use as the semiconducting material in thin‐film transistors (TFTs). To enhance the electrical performance of the devices, two different kinds of solution processing (spin‐coating and drop‐casting) on various gate dielectrics as well as additional post‐treatment are employed on thin films of TESPE‐ADT, and p‐channel OTFT transport with hole mobilities as high as ～0.12 cm² V^?1 s^?1 are achieved. The film morphologies and formed microstructures of the semiconductor films are characterized in terms of film processing conditions and are correlated with variations in device performance.     

Selective enrichment of catecholamines using iron oxide nanoparticles followed by CE with UV detection

This study examines the use of unmodified magnetite nanoparticles (Fe₃O₄ NPs) for selective extraction and enrichment of the catecholamines dopamine (DA), noradrenaline (NE), and adrenaline (E), prior to analysis using capillary electrophoresis with UV detection. Coordination between Fe³⁺ on‐the‐surface Fe₃O₄ NPs and the catechol moiety of catecholamines enables Fe₃O₄ NPs to capture catecholamines from an aqueous solution. We obtained maximum loading of catecholamines on the NP surface by adjusting the pH of the solution to 7.0. In addition, catecholamine loading on the Fe₃O₄ NPs increased in conjunction with NP concentrations. H₃PO₄ was found to be efficient for the removal of adsorbed catecholamines on the NP surface. Adding 1.2% poly(diallyldimethylammonium chloride) to the background electrolyte resulted in a baseline separation of the liberated catecholamines within 20 min. Under optimal extraction and separation conditions, the limit of detections at a S/N ratio of 3 for E, NE, and DA were 9, 8, and 10 nM, respectively. Significantly, the combination of a phenylboronate‐containing spin column and the proposed method was successfully applied to the determination of NE and DA in human urine and NE in Portulaca oleracea L. leaves.     

Topological analysis and charge density studies of an alpha-diimine macrocyclic complex of cobalt(II)--a combined experimental and theoretical study

A combined experimental and theoretical study of the paramagnetic [Co(II)(C12H20N8)(H2O)2] x 2 ClO4 complex was made on the basis of the electron density distribution and topological analysis. Accurate single-crystal diffraction data were measured on a suitable crystal with Mo(K alpha) radiation at 125 K. The CoII ion is coordinated in a square bipyramidal fashion with four imino nitrogen atoms at the equatorial plane and two water molecules at the axial positions. The hydrogen-bonding interaction at 125 K between the coordinated water molecule and the ClO(4)(-) ion makes the space group different from that at 298 K. Parallel MO calculations were made at UHF and DFT/UB3LYP. The agreement between experiment and theory is reasonably good. The chemical bonding characterization is presented in terms of the topological properties associated with bond critical points and the natural bond orbital (NBO) analysis as well. The Co-N(imino) and Co-O(water) bonds are dative bonds, where the lone-pair electrons of N or O serve as a -donor; however, a certain covalent character is identified in the Co-N(imino) bond. A delocalized C-N, N-N pi-bond model is proposed. The d-orbital energies of Co in this complex are such that E(d(xz)) is approximately equal to E(d(yz)) is approximately equal to E(dx(2-y2)) < E(d(z2)) < E(d(xy)); notice that d(xy) and d(z2) are d(sigma) orbitals in this case. The Co(II) ion is in a low-spin d7 state with the singly occupied d(z2) orbital. The asphericity in electron density at Co and Cl nuclei is nicely demonstrated by the Laplacian of electron density. The envelope plot of the isovalue Laplacian surface around the nucleus gives the exact shape of such asphericity. The isovalue Laplacian surfaces of these two nuclei show significantly different VSCC character in both experimental and theoretical results.     

Optical behaviour of photoimageable cholesteric liquid crystal cells with various novel chiral compounds

In theory, both polarity and steric hindrance are basic factors which affect molecular interactions. To investigate the optical properties and steric structures of chiral compounds having different chiral moieties which affect the wavelength of light reflection in liquid crystal (LC) cells, a series of novel chiral compounds and azobenzene derivatives were synthesized. The liquid crystalline phases of the compounds were identified using small angle X‐ray diffraction, differential scanning calorimetry and polarizing optical microscopy. Cholesteric LC cells with various synthesized chiral dopants which selectively reflect visible light were first prepared, the photochemical switching behaviour of colours was then investigated, with special reference to the change in transmittance in cholesteric LC cells containing an azobenzene derivative as a photoisomerizable guest molecule. Reversible isomerization of azobenzene molecules occurred in the cholesteric systems, resulting in a depression of T _ChI and a shift of the selectively reflected wavelength. We discuss the photochemically driven change in the helical pitch of the cholesteric LCs with respect to structural effects involving the chiral moieties. Molecular interactions caused by the added dopants, reliability and stability of the photoisomerization, and UV irradiation effects on the cholesteric LC cells were also investigated. A real image was recorded through a mask on a cholesteric LC cell fabricated in this investigation.