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Volumn 10, Issue 18, 2004, Pages 4422-4435

Electronic structures of zinc and palladium tetraazaporphyrin derivatives controlled by fused benzo rings

Author keywords

Cyolic voltammetry; Electronic structure; EPR spectroscopy; Luminescence; Macrocyclic ligands

Indexed keywords

AROMATIC COMPOUNDS; ELECTRONIC STRUCTURE; OXIDATION; PALLADIUM; PARAMAGNETIC RESONANCE; SPECTROSCOPIC ANALYSIS;

EID: 4944241895     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400328     Document Type: Article
Times cited : (79)

References (85)
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    • In the case of 2AdZn, 2OpZn, and 3Zn, the first oxidation couple is reversible, but the first oxidation couple of 4Zn seems to consist of two overlapping waves. Overlapping waves are often observed for aggregated Pcs. This was supported by CV measurements at various scan rates; the re-reduction wave at more anodic potential became more prominent at faster scan rates, while the less anodic counterpart diminished. Therefore, the more anodic wave is assigned to the monomer. The reduction couples are reversible except in the case of 2AdZn. H. Isago, C. C. Leznoff, M. F. Ryan, R. A. Metcalfe, R. Davids, A. B. P. Lever, Bull. Chem. Soc. Jpn. 1998, 71, 1039.
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    • For all the zinc complexes, very weak absorption bands are observed between the Soret and Q bands. For Pcs with alkoxyl groups, these absorption bands are assigned to n-π* transitions. This broad band is also seen for 0Zn, but not observed for tetra-tert-butylated ZnTAP. ZnTAR Therefore, the broad band of 0Zn originates from transitions related to phenyl groups. This is supported by the CI calculations, which show that transitions at around 400 nm become more intense with increasing number of phenyl groups (Figure 12). a) N. Kobayashi, A. B. P. Lever, J. Am. Chem. Soc. 1987, 109, 7433;
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    • (Eds.: K. M. Kadish, R. M. Smith, R. Guilard), Academic Press, New York, Chap. 103
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    • Mack, J.1    Stillman, M.J.2
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    • 4h symmetry, were first optimized under the ZINDO/1 method. For 1Zn, 2AdZn, 2OpZn, and 3Zn, structures with elimination of the fused benzo rings from the optimized Pc were employed. Methoxyl groups optimized by the MM+ method were used instead of long alkoxyl chains, and the dihedral angle between the TAP plane and phenyl groups was assumed to be 35° by reference to the X-ray structural data. While the electronic structures are influenced by the distortion of a porphyrin plane, it was confirmed by the PM3 calculations that the TAP skelton was optimized to be planar even with the substitutions. a) N. Kobayashi, T. Fukuda, K. Ueno, H. Ogino, J. Am. Chem. Soc. 2001, 123, 10740;
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 10740
    • Kobayashi, N.1    Fukuda, T.2    Ueno, K.3    Ogino, H.4
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    • 1 state was calculated under a half-point charge approximation employing the HOMO and LUMO coefficients obtained by the PPP calculations. [24] J. Higuchi, J. Chem. Phys. 1963, 38, 1237.
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  • 67
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    • note
    • 1y states.
  • 69
    • 4944249976 scopus 로고    scopus 로고
    • note
    • -5 M).
  • 75
    • 4944245886 scopus 로고    scopus 로고
    • note
    • 2 orbitals.
  • 77
    • 4944236175 scopus 로고    scopus 로고
    • note
    • -1 for OPd, 1Pd, 2AdPd, 2OpPd, 3Pd, and 4Pd, respectivelyl.[35] These Z values are slightly larger than those obtained experimentally,[31,32] but the structural dependence is low (within 10%).


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