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41.
K. Lochner H. Bassler L. Sebastian G. Weiser G. Wegner V. Enkelmann 《Chemical physics letters》1981,78(2):366-370
The photoconductivity of DCHD displays a maximum near 3.6 eV coinciding with the maximum of the So → S1 absorption of the carbazole group. It is attributed to a sensitization involving charge transfer from the excited chromophore to the chain. The rate constant for non-radiative decay of the carbazole singlet due to energy transfer to the chain is 1.6 × 1013 s?1, and for charge transfer ≈ 3 × 1011 s?1. 相似文献
42.
43.
A set of highly preorganized pyrazolate-bridged dimanganese complexes L(Mn)MnX have been prepared and structurally characterized. They can be described as hybrid organometallic/Werner-type systems that consist of a low-spin CpMn(I)(CO)2 subunit (Mn1) and a proximate tripodal tetradentate {N4} binding pocket accommodating a high-spin Mn(II) ion (Mn2), with Mn...Mn distances of approximately 4.3 A and different coligands bound to Mn2. Density functional theory (DFT) calculations (both the hybrid B3LYP and the pure BP86 functionals and the all-electron basis sets 6-311G and 6-311G*) confirm that the valence alpha and beta Kohn-Sham molecular orbitals (MOs) of these mixed-valent Mn(I)Mn(II) compounds have predominant Mn(3d) character and an almost perfectly localized nature: all five unpaired electrons are essentially localized at the Werner-type Mn2, whereas Mn1 possesses an effective closed-shell structure with the MOs of highest energy centered there. One-electron oxidation occurs in a clean process at approximately E(1/2) = -0.6 V (versus ferrocene/ferrocinium), giving the low-spin/high-spin Mn(II)Mn(II) species. UV/vis and IR spectroelectrochemistry as well as a detailed theoretical analysis reveal that the redox process takes place with strict site control at the organometallic subunit, while it does not significantly influence the spin and charge distribution on the Werner-type site. Positions and shifts of the nu(C[triple bond]O) absorptions are largely reproduced by the DFT calculations. These systems thus represent an exceptional example of the effect the unsymmetry of a dinucleating ligand scaffold has on the spin and charge distribution in homobimetallic complexes and might offer interesting prospects for the study of the cooperative effects of bimetallic arrays. 相似文献
44.
Sebastian G. Spain Matthew I. Gibson Neil R. Cameron 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2059-2072
Glycopolymers are receiving increasing interest due to their application in areas, such as glycomics, medicine, biotechnology, sensors, and separation science. Consequently, new methods for their synthesis are constantly being developed, with an increasing emphasis on the preparation of well-defined polymers and on the production of complex macromolecular architectures such as stars. This review covers recent developments in the synthesis of glycopolymers, with a particular emphasis on (i) the use of controlled radical polymerization to prepare well-defined glycopolymers from unprotected monomers and (ii) postpolymerization modification strategies using reactive polymer precursors (including “click” reactions). Recent work on the production of glycosylated polypeptides, which are under investigation as mimics of naturally occurring glycoproteins, is also included. The authors offer some suggestions as to future developments and remaining challenges in this topical area of polymer chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem45: 2059–2072, 2007 相似文献
45.
The three-dimensional structure of a complex tubular uranyl phosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, was determined ab initio from laboratory X-ray powder diffraction data and refined by the Rietveld method. The crystals belong to the space group P2(1)2(1)2(1), with a = 17.1966(2) ?, b = 7.2125(2) ?, c = 27.8282(4) ?, and Z = 4. The structure consists of three independent uranium atoms, among which two are seven-coordinated and the third is eight-coordinated. These metal atoms are connected by four different phosphonate groups to form a one-dimensional channel structure along the b axis. The phenyl groups are arranged on the outer periphery of the channels, and their stacking forces keep the channels intact in the lattice. The determination of this structure which contains 50 non-hydrogen atoms in the asymmetric unit, from conventional X-ray powder data, represents significant progress in the application of powder techniques to structure solution of complex inorganic compounds, including organometallic compounds. 相似文献
46.
Albrecht M Mirtschin S de Groot M Janser I Runsink J Raabe G Kogej M Schalley CA Fröhlich R 《Journal of the American Chemical Society》2005,127(29):10371-10387
The ligands 4-7-H(2) were used in coordination studies with titanium(IV) and gallium(III) ions to obtain dimeric complexes Li(4)[(4-7)(6)Ti(2)] and Li(6)[(4/5a)(6)Ga(2)]. The X-ray crystal structures of Li(4)[(4)(6)Ti(2)], Li(4)[(5b)(6)Ti(2)], and Li(4)[(7a)(6)Ti(2)] could be obtained. While these complexes are triply lithium-bridged dimers in the solid state, a monomer/dimer equilibrium is observed in solution by NMR spectroscopy and ESI FT-ICR MS. The stability of the dimer is enhanced by high negative charges (Ti(IV) versus Ga(III)) of the monomers, when the carbonyl units are good donors (aldehydes versus ketones and esters), when the solvent does not efficiently solvate the bridging lithium ions (DMSO versus acetone), and when sterical hindrance is minimized (methyl versus primary and secondary carbon substituents). The dimer is thermodynamically favored by enthalpy as well as entropy. ESI FT-ICR mass spectrometry provides detailed insight into the mechanisms with which monomeric triscatecholate complexes as well as single catechol ligands exchange in the dimers. Tandem mass spectrometric experiments in the gas phase show the dimers to decompose either in a symmetric (Ti) or in an unsymmetric (Ga) fashion when collisionally activated. The differences between the Ti and Ga complexes can be attributed to different electronic properties and a charge-controlled reactivity of the ions in the gas phase. The complexes represent an excellent example for hierarchical self-assembly, in which two different noncovalent interactions of well balanced strengths bring together eleven individual components into one well-defined aggregate. 相似文献
47.
48.
Werner Georg Nowak 《manuscripta mathematica》1982,39(2-3):277-285
Let G (R) denote the number of lattice points (,) **Z2 in the domain B(R) bounded by the lemniscate (x2+y2)2=2R2 (x2–y2) and put P(R)=G(R)-R2(R2 being the area of B(R)). The purpose of this paper is to determine the order of magnitude of P(R) for large R by proving the asymptotic relation (3). An analogous result is given for the eight curve x4=R2 (x2–y2). 相似文献
49.
Herbert Schumann Sebastian Dechert Frank Girgsdies Bernd Heymer Markus Hummert Ji‐Young Hyeon Jens Kaufmann Stefan Schutte Sonja Wernik Birgit C. Wassermann 《无机化学与普通化学杂志》2006,632(2):251-263
Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me2Al{μ‐O(CH2)3NMe2}]2 ( 1a ), Me2AlOC6H2(CH2NMe2)3‐2,4,6 ( 2a ), [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]2 ( 3a ) and [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NHCH2Ph}]2 ( 4 ) are formed by reacting equimolar amounts of AlMe3 and Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH2OH, or (S)‐PhCH2NHCH(i‐Pr)CH2OH, respectively. An excess of AlMe3 reacts with Me2N(CH2)2OH, Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH2OH producing the “pick‐a‐back” complexes [Me2AlO(CH2)2NMe2](AlMe3) ( 5 ), [Me2AlO(CH2)3NMe2](AlMe3) ( 1b ), [Me2AlOC6H2(CH2NMe2)3‐2,4,6](AlMe3)2 ( 2b ), and [(S)‐Me2AlOCH2CH(i‐Pr)NH‐i‐Pr](AlMe3) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 6 ) and [{CH2=C(CH3)}(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 8 ) are to obtain from Me2AlCl and Me2N(CH2)2OH and from [Cl2Al{μ‐O(CH2)2NMe2}]2 ( 7 ) and CH2=C(CH3)MgBr, respectively. The analogous dimethylgallium alkoxides [Me2Ga{μ‐O(CH2)3NMe2}]2 ( 9 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]n ( 10 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NHCH2Ph}]n ( 11 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)N(Me)CH2Ph}]n ( 12 ) and [(S)‐Me2Ga{μ‐OCH2(C4H7NHCH2Ph)}]n ( 13 ) result from the equimolar reactions of GaMe3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, 1H‐, 13C‐ and 27Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction. 相似文献
50.