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  • 1
    ISSN: 1573-4994
    Keywords: Acid-base behavior ; photometry ; fluorimetry ; 2,2′-diquinolyl ; 2,2′,2″-terpyridyl
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract A photometric and fluorimetric study of the acid-base behavior of 2,2′-diquinolyl and 2,2′,2″-terpyridyl was performed. In sulfuric acid medium, the doubly charged 2,2′-diquinolynium ion undergoes the first dissociation atH 0=0.20±0.09, as determined by fluorimetry (λex=336 nm, λem=424 nm). Photometric titration is less accurate because of the overlapping of the absorption spectra. The second dissociation constant of 2,2′-diquinolyl was determined by fluorimetric titration (λex=336 nm, λem=420 nm), obtaining a value of 3.67±0.03. The triply charged 2,2′,2″-terpyridyl molecule was found to undergo the first dissociation atH 0=−7.17±0.04, as determined by fluorimetric titration (λex=316 nm, λem=350 nm), in aqueous sulfuric acid medium. Photometric titration (λ=335 nm) was performed in the presence of 6.5% ethanol because of the low solubility of the compound in water. In this ethanolic∶water medium, a value of the dissociation constant atH 0=−7.39±0.03 was calculated. The second dissociation constant was determined to be 2.81±0.12 by photometric titration at 285 nm, and values of 4.03±0.26 and 4.16±0.20 were found for the third dissociation constant by photometric titrations at 320 and 295 nm, in 10% ethanol, in close agreement with previously reported values. The fluorimetric titration profile obtained by exciting at 274 nm and measuring the fluorescence emission at 350 nm, in the zone betweenH 0=−3 and pH=10, is complicated by the several equilibria involved.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-6036
    Keywords: 36.40.+d ; 74.75.+t ; 79.60.−i
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract The electronic structure of K-doped C60 was investigated by photoemission (PE) and X-ray absorption near-edge structure (XANES) studies at the C-1s and K-2p thresholds. In addition, information on the local K-derived partial density of states in superconducting K3C60 was obtained by resonant PE at the K-2p 1/2 threshold. The experimental observations support a complete charge transfer from K to C60 and we clearly observe a finite density of states atE F . From resonant PE, occupied states with K-p, d character could be identified in the binding-energy region from 1.5 to 8 eV below, but not directly at the Fermi level. This partial-density-of-states structure agrees well with the results of our band-structure calculations based on the local-density approximation.
    Type of Medium: Electronic Resource
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