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61.
Benniston AC Harriman A Romero FM Ziessel R 《Dalton transactions (Cambridge, England : 2003)》2004,(8):1233-1238
The photophysical properties of closely-coupled, binuclear complexes formed by connecting two ruthenium(II) tris(2,2'-bipyridine) complexes via an alkynylene group differ significantly from those of the relevant mononuclear complex. In particular, the energy of the first triplet excited state is lowered relative to the parent complex, because of the presence of the alkynylene substituent, while the triplet lifetime is prolonged, in part, because of extended electron delocalization. We now report that the triplet lifetime is also affected by the nature of the spectator 2,2'-bipyridyl ligands. Thus, replacing the parent 2,2'-bipyridine ligands with the corresponding 4,4'-dinitro-substituted ligands serves to decrease the luminescence yield and lifetime. With the corresponding carboxylate ester, the luminescence yield and lifetime are increased. Perdeuteration of the parent 2,2'-bipyridine ligands also leads to a modest increase in the luminescence yield. Such observations are indicative of electronic coupling between the various metal-to-ligand, charge-transfer excited triplet states. Temperature dependence studies confirm that these excited states are closely spaced and thermally accessible at ambient temperature. For some of the binuclear complexes, the quantum yield for formation of the lowest-energy triplet state is significantly less than unity. 相似文献
62.
A quantitative compressed pellet infrared method used together with a micro-distillation to effect separation of the isomer has been developed and reported here for the analysis of ortho-, meta-, and para-terphonyl. The terphenyl content is determined on fractions isolated by distillation from radiation damaged samples. The compressed pellet infrared method is preferred instead of the more conventional solution technique since smaller quantities of isolated terphcnyl are required. The pellet method is applicable also to polyphenyls higher than the terphenyls. The solution technique is not due to the insolubility of the polyphenyls. It is expected that the compressed pellet spectral method developed here might well find application in the analysis of compounds other than polyphenyls. Results presented here appear to be the, first quantitative infrared data reported in the literaturu on polyphenyl compounds. 相似文献
63.
The solution conformation of bicyclo [3.1.0] hexan-3-one has been obtained by the use of the shifts induced in its 1H and 13C NMR by Yb(fod)3. Refinement of the angle of pucker, ∝, of the 5-membered ring indicates that the molecule adopts a flattened boat conformation with ∝ = 195°. This prediction is supported by ab initio, STO-3G, calculations on the isolated molecule. Use of a two- or four-site model for lanthanide-substrate complexing adequately reproduces the experimental data whereas a one-site binding model is unsatisfactory. The importance of multi-site binding is further emphasised by results for the C2v-symmetric ketone, adamantanone, where only a four-site model gives satisfactory agreement between observed and calculated lanthanide-induced shifts. 相似文献
64.
Joseph F. Chiang Raymond Chiang K.C. Lu Eun-Mo Sung Marlin D. Harmony 《Journal of Molecular Structure》1977,41(1):67-77
The molecular structure of norbornene has been investigated in the gas phase by combining electron diffraction data with microwave spectroscopic rotational constants. The interatomic distances (rg) and bond angles were obtained by applying a least squares program to the refined experimental molecular diffraction intensities. The CC bond length was found to be 1.336 ± 0.002 Å while the ) bond length was 1. 529 ± 0.007 Å. Other bond lengths and angles included (IUPAC numbering system was used for norbornene): C1-C6 = 1.550 ± 0.020 Å, C1-C7 = 1.566± 0.005 Å, C5-C6 = 1.556 ± 0.005 Å, C-Have. = 1.103 ± 0.003 Å, ∠C1C2C4 = 95.3°. The dihedral angle between planes C1C2C3C4 and C1C6C5C4 is 110.8 ± 1.5° while that between C1C2C3C4 and C1C7C4 is 122.3°. The moments of inertia calculated from ED structure are in good agreement with microwave spectroscopic values. 相似文献
65.
Raymond Zelnik Ema Rabenhorst Akhtar Haider Jürgen Lauterwein Hugo Wyler 《Helvetica chimica acta》1983,66(3):780-788
Dehydration of abiet-8-ene-7β, 13β-diol (ibozol, 1 ) leads to abieta-7,9(11)-dien-13β-ol ( 2 ) which aromatizes slowly to the known abieta-8,11,13-triene ( 3 ). Photosensitized oxygenation of the heteroannular diene 2 yields a mixture from which three compounds were identified; abiet-7-ene-9α, 11α, 13β-triol ( 4 ), abieta-8,11,13-trien-7-one ( 5 ), and abieta-8,11,13-trien-7α-ol ( 6 ). 相似文献
66.
The synthesis of the novel naphtho[2′,1′:4,5]thieno[2,3-c]quinoline (11) ring system and four of the isomeric monomethyl derivatives is described. 相似文献
67.
The effects of hydrodynamic interactions on the friction tensors for two particles in solution are studied. The particles have linear dimensions on nanometer scales and are either simple spherical particles interacting with the solvent through repulsive Lennard-Jones forces or are composite cluster particles whose atomic components interact with the solvent through repulsive Lennard-Jones forces. The solvent dynamics is modeled at a mesoscopic level through multiparticle collisions that conserve mass, momentum, and energy. The dependence of the two-particle relative friction tensors on the interparticle separation indicates the importance of hydrodynamic interactions for these nanoparticles. 相似文献
68.
Bronger RP Silva SM Kamer PC van Leeuwen PW 《Dalton transactions (Cambridge, England : 2003)》2004,(10):1590-1596
A highly active and regioselective catalyst obtained from a novel dicationic ligand (1) and Rh(CO)2(acac) for hydroformylation of 1-hexene and 1-octene in ionic liquids is reported. Optimisation studies of various reaction parameters led to an unprecedentedly active (TOFs > 6200 mol mol(-1) h(-1), T= 100 degrees C), selective (l/b ratios > 40) and stable hydroformylation procedure. No catalyst leaching (Rh-loss < 0.07% of initial rhodium intake, P-loss < 0.4% of the initial phosphorus intake) or losses in performance could be measured during 1-octene hydroformylation recycle experiments in 1-butyl-3-methylimidazolium hexafluorophosphate. At low catalyst loadings activities and regioselectivities competitive with one-phase catalysis in conventional solvents were observed. At high catalyst loadings the system is extremely stable and has a long shelf-life as a result of the formation of stable, if inactive rhodium dimers. 相似文献
69.
70.
The dorid nudibranch Archidoris odhneri produces (all E)-2,3-dihydroxypropylfarnesate and its two monoacetoxy derivatives. 相似文献