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  • Porphyrin-quinone cyclophanes  (6)
  • Intramolecular electron transfer  (3)
  • 21.10.Ft  (2)
  • Radical cations  (2)
  • 1
    ISSN: 1434-601X
    Keywords: 21.10.Ft ; 25.70.Np ; 27.40.+Z
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract At the projectile-fragment separator FRS of GSI, relativistic secondary beams of about 520 MeV/nucleon were produced by fragmentation of a primary beam of58Ni at 650 MeV/nucleon in a beryllium target. By means of aΔE—Bρ—TOF measurement, the fragments have been identified and their charge-changing probabilities in targets of CH2, C, Al, and Pb have been determined. We describe the results for the total charge-changing cross sections in this first paper, whereas a second article deals with the partial charge-changing cross sections. At the drip line, the measured charge-changing cross sections exhaust close to 100% of the total interaction cross sections as calculated with semiempirical models. The measurements at the proton drip line with low-Z targets indicate that only a very small increase of the cross sections may be observed, whereas the measurements with a lead target show that no significant increase of the total charge-changing cross sections is present which would be a hint for low-lying dipole strength. Our experimental data are compared to Glauber-type calculations.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-601X
    Keywords: 21.10.Ft ; 25.70.Np ; 27.40.+z
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract At the projectile-fragment separator FRS of GSI, relativistic secondary beams of about 520 MeV/nucleon were produced by fragmentation of a primary beam of58Ni at 650 MeV/nucleon in a beryllium target. By means of aΔE—Bρ—TOF measurement, the fragments were identified and their charge-changing probabilities in targets of (CH2) n , C, Al, and Pb placed at the exit of the FRS were determined. Whereas a first article dealt with the total charge-changing cross sections, we describe in this second article the element distributions of these secondary fragments, which are found to depend strongly on the isospin of the secondary projectile as well as on the target material. In the case of the lead target, the influence of the electromagnetic dissociation is clearly visible in the one-proton and two-proton removal channels. The preference for the formation of even-Z fragments is much more pronounced for exotic secondary projectiles than for projectiles close to stability. Calculations with a geometrical abrasion-ablation model allow to understand the global features of the experimental data. However, far from stability, the discrepancies between calculations and experimental data increase.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1434-193X
    Keywords: Paracyclophanes ; Cyclic voltammetry ; Radical cations ; ESR/ENDOR spectroscopy ; Intramolecular electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A range of [n.n]paracyclophane radical cations (4·+-12·+), in which two 2,5-dimethoxy-1,4-phenylene units are connected by alkano bridges of varying length, have been studied by ESR and ENDOR spectroscopy. In the [2.2]- and [3.3]paracyclophane radical cations 4·+-6·+, 10·+ and 11·+ the delocalization of the unpaired electron over both π-moieties and the distinct difference between the first and second oxidation potentials, ΔE = E20 - E10, are evidence for a strong intramolecular electronic interaction between the two electrophores. The [5.5] and [7.7] species (8·+ and 9·+) are localized radical cations at low temperature (ca. 220 K). At room temperature, the higher molecular flexibility leads to a significant increase in the number of internal collisions between the electrophores, resulting in a fast (ESR time scale) intramolecular electron transfer. The intermediate [4.4]paracyclophane radical cations 7·+ and 12·+ are apparently also localized radical cations. The close interplanar distance between the two π-moieties, however, facilitates their mutual contacts. In 7·+, the intramolecular electron transfer becomes fast on the ESR time scale at room temperature; in 12·+ the transfer is fast over the temperature range 200-300 K.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1434-193X
    Keywords: 1,4-Benzoquinones ; [2.2]Paracyclophanes ; 1,4,8,11-Pentacenetetrones ; Cyclic voltammetry ; Radical anions ; ESR/ENDOR spectroscopy ; Intramolecular electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three types of tetrone radical anions in which two 1,4-benzoquinone units are connected by ethano (1·-, 2·-), [2.2]paracyclophane (3·-, 4·-), and anthracene bridges (5·-, 6·-) have been studied by ESR and ENDOR spectroscopy. The displacement of the unpaired electron over the two π moieties in the [2.2]cyclophane radical anions 1·--4·- and the marked difference between the first and second reduction potentials, ΔE = |E20 - E10| ≥ 0.20 V, are evidence for a substantial intramolecular electronic interaction between the two electrophores. Similar ΔE data for the syn- (3) and anti-naphthalenophanes (4) indicate that most of the intramolecular electronic interaction takes place through the [2.2]paracyclophane bridge. When ion pairing is inhibited by complexation of the cation, the unpaired electron in 5·- and 6·- is also delocalized over the whole pentacenetetrone system at temperatures as low as 160 K.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1434-193X
    Keywords: [2.2](1,4)Naphthalenophanes ; [2.2](1,4)Anthracenophane ; Pentacene ; Cyclic voltammetry ; Radical cations ; ESR/ENDOR spectroscopy ; Intramolecular electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various radical cations, in which two terminal 1,4-dimethoxybenzene units are anellated to [2.2]paracyclophane (2b•+, 3b•+), [2.2](1,4)naphthalenophane (4d•+), and anthracene bridges (5•+), have been studied by ESR and ENDOR spectroscopy. In the syn- and anti-naphthalenophane radical cations 2b•+ and 3b•+ the delocalization of the unpaired electron over both π-moieties and the distinct difference between the first and second oxidation potentials, ΔE = E20 - E10, are evidence for a substantial intramolecular electronic interaction between the two electrophores. Extension of the bridge in 4d•+ and 5 by benzo anellation results in a localized radical cation. Strong intramolecular electronic interaction between the two electrophores is found in the 1,4,8,11-tetramethoxy-pentacene radical cation (5•+). The syntheses of 4d are described.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0009-2940
    Keywords: Photosynthesis models ; Photoinduced electron transfer ; Porphyrin-quinone cyclophanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To study the structure dependence of photoinduced electron transfer between porphyrins and quinones the concept of a new family of porphyrin-quinone cyclophanes with vertical arrangements of porphyrin and quinone units is presented. The syntheses of the quinone-porphyrin-quinone cyclophane 1, the prototype of this series, and of the quinone-porphyrindonor cyclophanes 12 and 14 are described. Spectroscopic data are discussed with regard to the structures involved and in relation to electron-transfer reactions occurring in these systems.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0009-2940
    Keywords: Porphyrin-quinone cyclophanes ; Photoinduced electron transfer in porphyrin-quinone cyclophanes ; Absorption and emission spectra of porphyrin-quinone cyclophanes ; Redox potentials and electron transfer in intramolecular porphyrin-quinone systems ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absorption and emission spectra of the doubly quinone-bridged porphyrin cyclophanes 1-4 with gradually varied acceptor strength as well as of the single-bridged analogues 5-9 and 10-13 are reported. Reduction and oxidation potentials of these intramolecular porphyrin-quinone systems have been determined. Based on these data, fluorescence quenching as well as time-resolved fluorescence lifetime measurements are discussed in terms of photoinduced electron transfer to the charge-separated zwitterionic state.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 231-236 
    ISSN: 0009-2940
    Keywords: Zinc porphyrin complexes ; Porphyrin-quinone cyclophanes ; Photoinduced electron transfer ; Electron-transfer mechanism in metalloporphyrin-quinone cyclophanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to increase the driving force for photoinduced electron-transfer reactions of porphyrin-quinone cyclophanes, the zinc complexes 3a-e and 4a-e were prepared from the corresponding cyclophanes of the 1 and 2 series. Electron-transfer-related properties like redox potentials and fluorescence spectra were determined for 3a-e and 4a-e. The X-ray structure analysis of 4a indicates that for the very fast and solvent-independent electron transfer in these systems a specific mechanism involving an interaction of a quinone carbonyl group with the zinc might be considered as an alternative to through-space electron-transfer.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0009-2940
    Keywords: Porphyrin-quinone cyclophanes ; Photoinduced electron transfer ; Porphyrin cyclophane syntheses ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For studying intramolecular electron-transfer reactions, three groups of double- and single-bridged porphyrin-quinone cyclophanes 1-4, 5-9, and 11-14, resp., with gradual variation of quinone acceptor strengths were synthesized. As key intermediates for building up the porphyrin-cyclophane skeleton the correspondingly 3,6-substituted 1,4-bis[4-(2-formylphenyl)-butyl]-2,5-dimethoxybenzenes 15-20 were synthesized. Condensation with pyrrole yielded the doubly bridged porphyrin cyclophanes 42-45; via the bis(dipyrrolylmethyl) derivatives 46-51 and 64-67 the single-bridged porphyrin cyclophanes 58-63 and 72-75 were obtained by acidic condensation with triethyl formate. Cleavage of the methoxy groups and oxidation yielded the corresponding porphyrin-quinone systems. Some magnesium and zinc complexes of these cyclophanes are described. Spectroscopic data (MS, 1H NMR) are reported in support of the proposed structures.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 223-229 
    ISSN: 0009-2940
    Keywords: Porphyrin-quinone cyclophanes ; Photoinduced electron transfer ; Absorption and emission spectra of porphyrin-quinone cyclophanes ; Photosynthesis models ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses and spectroscopic properties of the porphyrin-quinone cyclophanes 1, 2 and 3 of which structural and/or conformational studies have recently reported[1] are described. Physical properties related to photoinduced electron-transfer reactions like redox potentials, absorption and emission spectra were determined for these compounds.
    Type of Medium: Electronic Resource
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