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Volumn 125, Issue 5, 2003, Pages 1253-1268

Origin of the red shifts in the optical absorption bands of nonplanar tetraalkylporphyrins

Author keywords

[No Author keywords available]

Indexed keywords

DECOMPOSITION; DEFORMATION; LIGHT ABSORPTION; NUCLEAR MAGNETIC RESONANCE; PROTEINS; RAMAN SCATTERING; ULTRAVIOLET RADIATION;

EID: 0037419841     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0280933     Document Type: Article
Times cited : (262)

References (77)
  • 30
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    • NSD data for more than 1500 hemes of protein structures contained in the Protein Data Bank are available in reference 29
    • NSD data for more than 1500 hemes of protein structures contained in the Protein Data Bank are available in reference 29.
  • 31
    • 0345891727 scopus 로고    scopus 로고
    • A web-based version of the NSD program is available at. Sun, L.-S.; Jentzen, W.; Shelnutt, J. A., Sandia National Laboratories: Albuquerque, NM
    • A web-based version of the NSD program is available at http://jasheln.unm.edu. Sun, L.-S.; Jentzen, W.; Shelnutt, J. A., Sandia National Laboratories: Albuquerque, NM, 2002.
    • (2002)
  • 35
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    • Universität Göttingen
    • Sheldrick, G. M., Ed., Universität Göttingen, 1994.
    • (1994)
    • Sheldrick, G.M.1
  • 36
    • 0004150157 scopus 로고    scopus 로고
    • Structure Determination Software Programs; Bruker Analytical X-ray Instruments Inc.: Madison, WI
    • Sheldrick, G. M., Ed., SHELXTL-Plus, Version 5.1: Structure Determination Software Programs; Bruker Analytical X-ray Instruments Inc.: Madison, WI, 1998.
    • (1998) SHELXTL-Plus, Version 5.1
    • Sheldrick, G.M.1
  • 45
    • 0345891723 scopus 로고    scopus 로고
    • Ph.D. Thesis, University of California at Davis
    • Nelson, N. Y., Ph.D. Thesis, University of California at Davis, 2000.
    • (2000)
    • Nelson, N.Y.1
  • 48
    • 0002643550 scopus 로고
    • Smith, K. M., Ed.; Elsevier: Amsterdam
    • Hoard, J. L. In Porphyrins and Metalloporphyrins; Smith, K. M., Ed.; Elsevier: Amsterdam, 1975; p 317.
    • (1975) Porphyrins Metalloporphyrins , pp. 317
    • Hoard, J.L.1
  • 49
    • 0346522523 scopus 로고    scopus 로고
    • note
    • Most of the in-plane deformation found in the NSD analysis (Tables S8 and S9) trivially results from the out-of-plane deformations, as illustrated in Figure 6. For a nonplanar porphyrin, the projections of the atomic positions into the ring mean plane, when expressed by NSD in terms of the equivalent in-plane vibrational mode displacements, can appear to be significant even though the porphyrin bonds and angles do not change much. In fact, the NSD in-plane deformations would occur even if there were no changes in bond length and only the bond angle changes necessary to accommodate the out-of-plane distortion. In contrast, IPNR represents structural changes due to a direct substituent effect. In the NSD analysis, IPNR appears as additional small normal mode displacements caused by substituent-induced internal strain; the IPNR displacements will appear along only in-plane modes for planar porphyrins but along both the inplane and out-of-plane modes for nonplanar porphyrins.
  • 51
    • 0346522522 scopus 로고    scopus 로고
    • note
    • 1u modes (see Figure S2).
  • 53
    • 0345891722 scopus 로고    scopus 로고
    • note
    • g orbitals probably results from orbital mixing.
  • 54
    • 0345891721 scopus 로고    scopus 로고
    • note
    • π orbital overlaps or if they involve the σ-electron system as well.
  • 55
    • 0345891720 scopus 로고    scopus 로고
    • note
    • 7)P that may not exist in other environments such as in solution.
  • 62
    • 0345891719 scopus 로고    scopus 로고
    • note
    • 56
  • 63
    • 0347152853 scopus 로고    scopus 로고
    • note
    • An important additional feature of the series of bridled porphyrins is that IPNR, if it is not negligible, should be largest for the short straps because they force the bulky substituents nearer to the mean plane and, consequently, to interact more strongly with the macrocycle atoms than for long straps, which relax these repulsive interactions by out-of-plane deformation. This stronger interaction with the macrocycle for the short straps must take place within a more planar macrocycle, leading to greater IPNR. Thus, if IPNR were important and caused a significant red shift, then we would expect the largest red shift for the short straps and the more planar porphyrin, contrary to the observed trend in the UV - visible data (Figure 8A and Table S13).
  • 65
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    • Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA, Vol.
    • Spiro, T. G. In Iron Porphyrins; Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA, 1982; Vol. Part II, p 89.
    • (1982) Iron Porphyrins , Issue.PART II , pp. 89
    • Spiro, T.G.1
  • 66
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    • note
    • m bond length through the α carbon. Nevertheless, even this correlation is somewhat indirect.
  • 68
    • 0346522518 scopus 로고    scopus 로고
    • note
    • For a series of metals in a nonplanar porphyrin, the slope of the core-size correlation depends on the intrinsic nonplanarity of the porphyrin ligand.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.