First principles study of the structure,electronic state,and stability of CmN2 clusters

Geometric and electronic properties of C_mN₂ (m = 1–14) clusters have been investigated by density functional theory using the hybrid B3LYP functional and the 6‐311G(d) basis set. Harmonic frequencies for these clusters are given to aid in the characterization of the ground states. These results show that C_mN₂ (m = 1–14) clusters form linear structures with D_∞h symmetry. Two N atoms favor to bond at ends in linear isomers. The chains with odd m have triplet ground states whereas the ones with even m have singlet ground states. The calculated HOMO–LUMO gaps and ionization potentials all show that the C_mN₂ (m = 1–14) clusters with even m are more stable than those with odd m, which is consistent with the observed even–odd alternation of the time‐of‐flight signal intensities. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Electronic structure and molecular orbital study of the first excited state of the high‐efficiency blue OLED material bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex from ab initio and TD‐B3LYP

Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq₂OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq₂OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq₂OH have been analyzed systematically to study the electronic transition mechanism in AlMq₂OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq₂OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S₁) of AlMq₂OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S₀ → S₁) of AlMq₂OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq₂OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al³⁺. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq₂OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Electrocatalytic oxidation of reduced nicotinamide coenzymes by graphite electrodes modified with an adsorbed phenoxazinium salt,meldola blue

Meldola Blue (7-dimethylamino-1,2-benzophenoxazine) can be adsorbed on graphite to give chemically modified electrodes. The electrochemical redox reactions of the phenoxazine are fairly reversible at low coverages with an E′^o of ?175 mV vs. SCE at pH 7.0. The electrode was most stable in acid solutions, at pH 6.0 its electrochemical activity decreased by 15% during 2h. The adsorbed compound mediated electron transfer in the electrocatalytic oxidation of the nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between Meldola Blue and the coenzyme is demonstrated by experiments with a rotating disk electrode. The complex decomposes in a rate limiting step (k₊₂=30 s^?1) to the oxidized coenzyme and the reduced Meldola Blue. The latter can be reoxidized in a fast electrochemical step. The overall result is an electrocatalytic oxidation at a voltage which is about 500 mV lower than at an unmodified electrode.     

Hydrothermal Synthesis and Structure of a New 3D Lanthanide—Carboxylate Framework,[La（btec）1／2（H2btec）1／2（H2O）]n（H4btec=1,2,4,5—Benzeneteracarboxylic acid）

The title complex, [La(btec)_1/2(H₂btec)_1/2 (H₂O)]_n (H₄btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO₃)₃·6H₂O in H₂O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm³, Z = 2, and final R = 0.0274, R_w = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H₄btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.     

A High－efficiency Preparation, Properties and Structure of （R, S ）－and （ S, S）－Pyrrolidine－2－carboxylic Acid 3,5－Dioxa－4－boracvclo.hepta [ 2,1－α; 3,4－α′] dinaphthalen－4－yl Esters

A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.     

Extrudate swell behavior of PS and LLDPE melts in a dual die with mixed circular/slit flow channels in an extrusion rheometer

Extrudate swell behaviors of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts in a dual channel die, having mixed circular/slit flow channels, in a constant shear rate rheometer were examined. The extrudate swell ratio for PS melt was observed to be higher than that for LLDPE melt for all cases, this being associated with the differences in molecular structures that could be described in terms of power law indexes and secondary flows near the die entrance. In single channel die, the extrudate swell of both PS and LLDPE melts in circular flow channel die was greater than that in slit flow channel, whereas, in dual channel die the slit channel exhibited a higher extrudate swell ratio, the results being explained by revealing the flow patterns of the melt in the barrel and die of the rheometer. It was found that the dimensionless size of the vortex flows near the entrance, and the extent of disentanglement of molecular chains on entering the die were the important factors for the differences in the extrudate swell ratios of the melts at the die exit influenced by the die designs used. Copyright © 2003 John Wiley & Sons, Ltd.     

Selective Transport of Alkali—Metal Cations through Liquid Membranes by Non—Cyclic Carriers

The emission spectra of a series of naphthalene end-labeled oligo-oxyethylene(N-Pn-N) and their facilitated transport of cations across liquid membranes have been investigated.Alkali-metal cations enhance or inhibit the intramolecular excimer formation of N-Pn-N remarkably,suggesting that the polyether chain of N-Pn-N in solution complexes with the cations,and the orientation of the terminal chromophores depends on the cation size and the length of the polyether chain. These compounds are able to act as carriers to facilitate transport of alkali-metal cations through organic liquid membranes.The transport efficiencies are comparable with those of cyclic carriers such as crown ethers,and show remarkable selectivity.     

苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响

New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature.     

Design and Synthesis of 3‐Aryl‐5‐Alicylic‐[1,2,4]‐oxadiazoles as Novel Platelet Aggregation Inhibitors

A series of 4‐[2‐(alicyclic‐[1,2,4]oxadiazol‐3‐yl)phenoxy]‐butyric acids were synthesized from N‐hydroxy‐2‐isopropoxy benzamidine in 4 steps with good yields. These [1,2,4]oxadiazoles are novel platelet aggregation inhibitors preventing human platelet aggregation induced by thromboxane derivative U44,619 and adenosine diphosphate. A structure‐activity‐relationship study revealed that the potency for these 5‐oxadiazoles increases with the increase in the ring size of the alicylic rings. Derivative 8f may be useful as a template for the design of more potent anti‐platelet agents.     

The Structure of Bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium in the Solid State and in Solution

The complex, bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium, Pd[(S)‐APCS]₂, 1 , was prepared by reaction of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine with PdCl₂ in THF. Complex 1 has been characterized by spectroscopic methods and its structure has been determined by X‐ray crystallography. Crystal data: space group C2, a= 16.082 (2), b = 17.104 (2), c = 13.051 (2)Å, β = 99.95 (1)°, V = 3535.9 (8) ų, Z = 2 with final residuals R1 = 0.0491 and wR2 = 0.0944. Two independent molecules, (S,S)‐Pd[(S)‐APCS]2, 1a , and (R,R)‐Pd[(S)‐APCS]2, 1b , were found in each asymmetric unit, which exchange to each other via a series of nitrogen inversion and C‐C bond rotation. The inversion energy (ΔGc₁^≠) and the energy barrier (δGc₂^≠) were 11.5 ± 0.1 Kcal mol^?1 at 246 K and 9.8 ± 0.1 Kcal mol^?1 at 199 K, respectively, calculated by dynamic NMR data.