Orbital-resolved partial charge transfer from the methoxy groups of substituted pyrenes in complexes with tetracyanoquinodimethane--a NEXAFS study

It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds and their electronic properties. Microcrystals of tetra-/hexamethoxypyrene as donors with the strong acceptor tetracyano-p-quinodimethane (TMP/HMP-TCNQ) were grown by vapor diffusion. The oxygen and nitrogen K-edge spectra are spectroscopic fingerprints of the functional groups in the donor and acceptor moieties, respectively. The orbital selectivity of the NEXAFS pre-edge resonances allows us to precisely elucidate the participation of specific orbitals in the charge transfer process. Upon complex formation, the intensities of several resonances change substantially and a new resonance occurs in the oxygen K-edge spectrum. This gives evidence of a corresponding change of hybridization of specific orbitals in the functional groups of the donor (those derived from the frontier orbitals 2e and 6a(1) of the isolated methoxy group) and acceptor (orbitals b(3g), a(u), b(1g), and b(2u), all located at the cyano group) with π*-orbitals of the ring systems. Along with this intensity effect, the resonance positions associated with the oxygen K-edge (donor) and nitrogen K-edge (acceptor) shift to higher and lower photon energies in the complex, respectively. A calculation based on density functional theory qualitatively explains the experimental results. NEXAFS measurements shine light on the action of the functional groups and elucidate charge transfer on a submolecular level.     

Ω＋Ω→（ΩΩ）Jπ=0＋＋X Cross section Calculation

The cross sections of Ω+Ω→(ΩΩ)_J^π=0⁺+X are studied by using an effective Hamiltonian method. The results are σ_{Ω+Ω→(ΩΩ)0⁺+γ}=0.03～0.16×10^-29 cm² for p_Ω=100～400 MeV, and the cross sections of η production are about 10^-28 cm² for p_Ω > 880 MeV.     

α-Carbonyl Radical Cyclizatio n in Organic Synthesis

Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclic structures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones, underwent intramolecular radical cyclization smoothly to afford products 2.1, 2,3     

A GENERALIZATION OF BOYD'S INTERPOLATION THEOREM

Boyd's interpolation theorem for quasilinear operators is generalized in this pa-per,which gives a generalization for both the Marcinkiewicz interpolation theor...     

在乳液体系里制备过氧化氫基聚苯乙烯及其在接枝聚合上的应用

用不同分子量的聚苯乙烯在乳液体系中进行过氧化氢基化反应,然后测定这些产品的特性粘数,HPO值(每1,000个苯乙烯结构单元中所合的过氧化氢基平均数目)等。在过氧化氢基聚苯乙烯的红外光谱里,可以在3,200—3,600厘米~(-1)吸收区里观察到过氧化氢基的吸收带,其吸收强度随着HPO值的增大而加强。最后用这些大分子过氧化物引发甲基丙烯酸甲酯及苯乙烯聚合,得到接枝聚合物。经过分离提纯后,用下列的方法: (1)浊度滴定; (2)热机械性能的测试; (3)水解后测定交换量; (4)红外吸收光谱;证明它们是接枝共聚物。     

Design and Synthesis of Aviram–Ratner‐Type Dyads and Rectification Studies in Langmuir–Blodgett (LB) Films

The design and synthesis of Aviram–Ratner‐type molecular rectifiers, featuring an anilino‐substituted extended tetracyanoquinodimethane (exTCNQ) acceptor, covalently linked by the σ‐spacer bicyclo[2.2.2]octane (BCO) to a tetrathiafulvalene (TTF) donor moiety, are described. The rigid BCO spacer keeps the TTF donor and exTCNQ acceptor moieties apart, as demonstrated by X‐ray analysis. The photophysical properties of the TTF‐BCO‐exTCNQ dyads were investigated by UV/Vis and EPR spectroscopy, electrochemical studies, and theoretical calculations. Langmuir–Blodgett films were prepared and used in the fabrication and electrical studies of junction devices. One dyad showed the asymmetric current–voltage (I–V) curve characteristic for rectification, unlike control compounds containing the TTF unit but not the exTCNQ moiety or comprising the exTCNQ acceptor moiety but lacking the donor TTF part, which both gave symmetric I–V curves. The direction of the observed rectification indicated that the preferred electron current flows from the exTCNQ acceptor to the TTF donor.     

Spin-label HF-EPR of lipid ordering in cholesterol-containing membranes

Conventional oxazolidine spin-labelled lipids have the axial¹⁴N-hyperfine tensorz-axis directed along the long axis of the lipid chain. Investigation of lateral ordering of the lipids in membranes requires measurement of thex-y Zeeman anisotropy of the nonaxialg-tensor at high fields. Both the lateral and transverse ordering of the lipid chains in membranes of dimyristoyl phosphatidylcholine containing 40 mol% cholesterol in the liquid-ordered phase have been studied with 94 GHz electron paramagnetic resonance spectroscopy. This has been done by using probe amounts of phosphatidylcholine systematically spin-labelled at positionsn along the length of thesn- 2 chain [n-PCSL, 1-acyl-2-(n-(4,4-dimethyloxazolidine-N-oxyl) stearoyl)-sn-glycero-3-phosphocholine]. Nonaxial (g_xx?g_yy) anisotropy of the spin-labelled lipid chains is detected over a wide range of temperature throughout the liquid-ordered phase. The transverse profile of lateral ordering with position,n, of chain labelling follows the profile of the rigid steroid nucleus of cholesterol. It becomes progressively averaged towards the terminal methyl group of thesn- 2 chain, in the region of the flexible hydrocarbon chain of cholesterol. The nonaxial lipid ordering may be related to lipid domain formation in membranes containing cholesterol and saturated-chain lipids.