Synthesis, characterization and FET properties of novel dithiazolylbenzothiadiazole derivatives

Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility.     

OBSERVATION OF THE PICOSECOND TIME-RESOLVED SPECTRUM OF SQUID BATHORHODOPSIN AT ROOM TEMPERATURE

Difference spectra between squid rhodopsin and its bathorhodopsin at room temperature were measured ca. 150 ps and ca. 500 ps after the excitation at 347.2 nm by a double-beam picosecond time-resolved spectrometer. The spectra measured showed a red shift of the isosbestic point between squid rhodopsin and its bathorhodopsin and a lower ΔA_max/ΔA_min value compared with those measured at low temperatures by conventional spectrophotometry.     

Ruthenium-catalyzed arylation of 2-alkenylpyridines with aryl bromides: alternative E,Z-selectivity to Mizoroki-Heck reaction

Regio- and stereoselective arylation of 2-alkenylpyridines with aryl bromides is catalyzed by specific Ru(II)-phosphine complexes affording beta-arylated (Z)-2-alkenylpyridines, in which the aryl moiety is introduced cis to the pyridyl group. This geometrical selectivity is in sharp contrast to the Mizoroki-Heck reaction. [reaction: see text]     

Ab initio potential energy surfaces of the ion-molecule reaction: C2H2 + O+

High level ab initio calculations using complete active space self-consistent field and multi reference single and double excitation configuration interaction methods with cc-pVDZ (correlation consistent polarized valence double zeta) and cc-pVTZ (triple zeta) basis sets have been performed to elucidate the reaction mechanism of the ion-molecule reaction, C2H2(1Sigmag+) + O+(4S), for which collision experiment has been performed by Chiu et al. [J. Chem. Phys. 109, 5300 (1998)]. The minor low-energy process leading to the weak spin-forbidden product C2H2+ (2Piu) + O(1D) has been studied previously and will not be discussed here. The major pathways to form charge-transfer (CT) products, C2H2+ (2Piu) + O(3P) (CT1) and C2H2+ (4A2) + O(3P) (CT2), and the covalently bound intermediates are investigated. The approach of the oxygen atom cation to acetylene goes over an energy barrier TS1 of 29 kcal/mol (relative to the reactant) and adiabatically leads the CT2 product or a weakly bound intermediate Int1 between CT2 products. This transition state TS1 is caused by the avoided crossing between the reactant and CT2 electronic states. As the C-O distance becomes shorter beyond the above intermediate, the C1 reaction pathway is energetically more favorable than the Cs pathway and goes over the second transition state TS2 of a relative energy of 39 kcal/mol. Although this TS connects diabatically to the covalent intermediate Int2, there are many states that interact adiabatically with this diabatic state and these lead to the other charge-transfer product CT1 via either of several nonadiabatic transitions. These findings are consistent with the experiment, in which charge transfer and chemical reaction products are detected above 35 and 39 kcal/mol collision energies, respectively.     

Formation process of silver-polypyrrole coaxial nanocables synthesized by redox reaction between AgNO3 and pyrrole in the presence of poly(vinylpyrrolidone)

We have recently demonstrated a one-step process to fabricate silver-polypyrrole (PPy) coaxial nanocables (Chen, A.; Wang, H.; Li, X. Chem. Commun. 2005, 14, 1863). The formation process of silver-PPy coaxial nanocables is discussed in this article. It was found from the results of TEM and SEM images that large numbers of silver atoms were formed when AgNO3 was added to a pyrrole solution. Then silver atoms transform to silver-PPy nanosheets with regular morphology, which will connect together to be more stable. Silver-PPy nanocables will be able to grow at the expense of the silver-PPy nanosheets. Poly(vinylpyrrolidone) (PVP) plays crucial roles in this process: as a capping agent to form silver nanowires, and as a dispersant of pyrrole monomers, which can influence the site at which pyrrole monomer exists. On the basis of experimental analysis, the possible mechanism was proposed. Because of the effect of PVP, silver ions and pyrrole monomers are apt to be adsorbed at the [111] and [100] facets of silver nanosheets, respectively. Obvious polymerization will take place on the boundary of the [111] and [100] facets. The PPy layer stays stable on the [100] facets. Meanwhile, newly formed silver atoms and silver nanosheets will further ripen and grow on the [111] facets. In a word, the morphology of final products and the formation process are determined by the reaction site between AgNO3 and the pyrrole monomer, which is influenced by PVP.     

A highly cis-selective synthesis of 2-ethynylaziridines by intramolecular amination of chiral bromoallenes: improvement of stereoselectivity based on the computational investigation

The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by B3LYP density functional calculations together with the 6-31+G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.     

Preparation and properties of high transition temperature aromatic polyphosphonates by phase-transfer-catalyzed polycondensation of phenylphosphonic dichloride with bisphenols

Aromatic polyphosphonates of high molecular weights were prepared from phenylphosphonic dichloride and bisphenols having rigid ring structures by the two-phase polycondensation in organic solvent–aqueous alkaline solution system with phase-transfer catalyst at 0°C or below. The effects of reaction solvent and catalyst on the inherent viscosities of the polymers formed are studied. The glass transition temperatures of the polyphosphonates with biphenyl, phenylindane, and diphenylfluorene units are 120, 124, and 188°C, respectively. These polymers are self-extinguishing and are readily soluble in solvents such as N,N-dimethylacetamide, pyridine, tetrahydrofuran, and chloroform. They began to lose weight above 300°C in air. Copolyphosphonates from combinations of bisphenols and phenylphosphonic dichloride are also prepared and characterized.     

A practical synthesis of archaeosine and its base

A practical synthetic route to 7-formamidino-7-deazaguanosine (archaeosine), a hypermodified nucleoside observed in archaeal tRNA, has been developed, which involves the addition of hydroxylamine to the cyano group of 7-cyano-7-deazaguanosine (preQ₀-nucleoside) and a subsequent Pd-catalyzed hydrogenation. PreQ₀-nucleoside was obtained from an optimized β-selective glycosylation developed by Hocek et al. The corresponding archaeosine base was subsequently synthesized in high yield from its precursor 7-cyano-7-deazaguanine (preQ₀).     

Synthesis,Properties, and Redox Behavior of 1,1,4,4‐Tetracyano‐2‐ferrocenyl‐1,3‐butadienes Connected by Aryl,Biaryl, and Teraryl Spacers

Aryl‐substituted 1,1,4,4‐tetracyano‐1,3‐butadienes (FcTCBDs) and bis(1,1,4,4‐tetracyanobutadiene)s (bis‐FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro‐electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis‐FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi‐electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.