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Urs Lang 《Mathematische Zeitschrift》1992,210(1):581-592
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Urs P. Wild Hans J. Griesser Vo Dinh Tuan Jean F.M. Oth 《Chemical physics letters》1976,41(3):450-455
The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S2 → S0 emission. In addition, fluorescence from the S1 state can be observed in monofluoro [13] annulene by exciting into the S2 or directly into the S1 absorption. 相似文献
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The photoelectron spectrum of tetrakis (methylidene)cyclobutane ( 1 , ‘[4]radialene’) is reported. The electronic states of 1 + are assigned on the basis of model calculations and with reference to related systems. Jahn-Teller activity in the degenerate states is discussed. A failure of the simple LCBO-model for the π(eg)-orbital of 1 is noted and traced to the fact that this orbital, though having a symmetry-equivalent π*-counterpart, does not interact with it. This feature is confined to [4n]radialenes; their total π-energies are therefore higher than those of the other members. It is shown that radialenes, in principle, do not constitute a class analogous to that of the linear polyenes as inferred earlier. 相似文献
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On alkalinization of solutions of the chromiun(III)-aquo ion simple deprotonation takes place first. The degree of hydroxylation n OH however can be brought up to only about 1 (the exact value depending on the total concentration [Cr]t), before the uncharged complex Cr(OH)3(OH2)3 is precipitated. The structure of the very sparingly soluble complex (solubility ~10?7M ) is held together by hydrogen bonds of type I between the molecules, so that its formula may be written as Cr(OH)2H6/2-lattice. The formation of the well ordered structure is extremely fast. On aging, the metallic centers become connected by μ-hydroxo-bridges (type II) and the substances become amorphous and very insoluble. The dinuclear (H2O)4Cr(OH)2Cr(OH2)44+ behaves similar on deprotonation. Concerning the various equilibria constants see Table 1. 相似文献
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Monodisperse Linear and Cyclic Oligo[(R)-3-hydroxybutanoates] Containing up to 128 Monomeric Units Using benzyl ester/(tert-butyl)diphenylsilyl ether protection, (COCl)2/pyridine esterification conditions, and a fragment-coupling strategy (with H2/Pd-C debenzylation and HF · pyridine desilylation), linear oligomers of (R)-3-hydroxybutanoic acid (3-HB) containing up to 128 3-HB building blocks (mol. weight > 11 000 Da) are assembled (Schemes 1,2,5, and 6). In contrast to the previously employed protecting-group combination, and due to the low-temperature esterifying conditions, this procedure leads to monodisperse oligomers: all steps occur without loss of single 3-HB units. The product oligomers with two, one, and no terminal protecting groups (mostly prepared in multi-gram amounts) are characterized by all standard spectroscopic methods, especially by mass spectroscopy (Figs. 2 and 3), by their optical activity, and by elemental analyses. Cyclization of the oligo[(R)-3-hydroxybutanoic acids] with up to 32 3-HB units, using thiopyridine activation and CuBr2 for the ring closure, produces oligolides consisting of up to 128 ring atoms (Scheme 7). Mixed oligolides containing 3-HB and (R)-3-hydroxypentanoic units are prepared from the corresponding linear trimers, using Yamaguchi's method for the ring closure (Scheme 8 and Fig.4 (X-ray crystal structures of two folded conformers)). Comparisons of melting points (Table 1), of [α] values (Tables 2 and 3), of 1H-NMR coupling constants (Table 3), and of molecular volume/hydroxyalkanoate unit (Table 4) of linear and cyclic oligomer derivatives and of the high-molecular-weigh polymer show that the monodisperse oligomers appear to be surprisingly good models for the polymer. Besides this insight, our synthesis is supplying the samples to further test the role of P(3-HB) (ca. 140 units) as a component of complexes forming channels through cell-wall phospholipid bilayers. 相似文献
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Edwin Haselbach Urs Klemm Rudolf Gschwind Thomas Bally Laurant Chassot Stephan Nitsche 《Helvetica chimica acta》1982,65(8):2464-2471
The radical cations of indeno [2, 1-a]indene ( 1 ), stilbene ( 2 ) and 3, 5, 3', 5'-tetramethylstilbene ( 3 ) were prepared by γ-irradiation of the neutral precursors in an electron-scavenging matrix at 77 K . Their electronic spectra were recorded and compared to the photoelectron spectra ( PE .) of the neutral precursors. The results show that either the fourth or the fifth excited doublet state of the cations is of «Non-Koopmans» type, with specific doublet energy (D) D (2Bg)=2.74 eV ( 1 +), =2.59 eV ( 2 +), =2.49 eV ( 3 +). Remarkably, 1 + possesses two electronic states in the 2.7-2.8 eV energy range: 2Au («Koopmans»-type) and 2Bg («Non -Koopmans»-type). The «SDT»-equation \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm D} = \sqrt {{\rm S} \cdot {\rm T}} $\end{document} approximately connecting excited singlet (S) and triplet (T) states of a neutral alternant system with the excited doublet (D) states of its radical cation - provided e-promotion occurs For all three excited states between the same (paired) orbitals-is satisfyingly exemplified by 1 : S1 = 3.92 eV and T1= 2.06 eV for 1 , D4 or 5=2.74 eV for 1 +. 相似文献
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Urs P. Wild Tae-Kyu Ha Guido A. Raggio Hans U. Keller Peter O. Brunner 《Helvetica chimica acta》1975,58(3):696-706
An ab initio SCF calculation of 42 points of the energy hypersurface of the fluoronium ion is presented using a contracted F(5s/3p), H(2s) gaussian basis set. In its equilibrium structure a bond length of 1.812 a.u. and a HFH bond angle of 127.2° are predicted. The calculated vibrational frequencies for H2F+, HDF+, and D2F+ are in good agreement with the experimental data. 相似文献