Skip to main content
Journal cover image

Extreme electronic modulation of the cofacial porphyrin structural motif.

Publication ,  Journal Article
Fletcher, JT; Therien, MJ
Published in: Journal of the American Chemical Society
April 2002

The synthesis, electrochemistry, and optical spectroscopy of an extensive series of cofacial bis[(porphinato)zinc(II)] compounds are reported. These species were synthesized using sequential palladium-catalyzed cross-coupling and cobalt-mediated [2+2+2] cycloaddition reactions. This modular methodology enables facile control of the nature of macrocycle-to-macrocycle connectivity and allows unprecedented modulation of the redox properties of face-to-face porphyrin species. We report the synthesis of 5,6-bis[(5',5''-10',20'-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (1), 5,6-bis[(2'-5',10',15',20'-tetraphenylporphinato)zinc(II)]indane (2), 5-([2'-5',10',15',20'-tetraphenylporphinato]zinc(II))-6-[(5"-10'',20''-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (3), 5-([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(5' '-10' ',20' '-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (4), 5-(2'-5',10',15',20'-[tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(2''-5'',10'',15'',20''-tetraphenylporphinato)zinc(II)]indane (5), 5,6-bis([2'-5',15'-diphenyl-10',20'-(trifluoromethyl)porphinato]zinc(II))indane (6), and 5,6-bis([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))indane (7); 4-7 define the first examples of cofacial bis[(porphinato)metal] compounds in which sigma-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a beta-to-beta linkage topology. Cyclic voltammetric studies show that the electrochemically determined HOMO and LUMO energy levels of these cofacial bis(porphinato) complexes can be lowered by 780 and 945 mV, respectively, relative to the archetypal members of this class of compounds; importantly, these orbital energy levels can be modulated over well-defined increments throughout these wide potentiometric domains. Analyses of these cofacial bis[(porphinato)metal] potentiometric data, in terms of the absolute and relative frontier orbital energies of their constituent [porphinato]zinc(II) building blocks, as well as the nature of macrocycle-to-macrocycle connectivity, provide predictive electronic structural models that rationalize the redox behavior of these species.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

April 2002

Volume

124

Issue

16

Start / End Page

4298 / 4311

Related Subject Headings

  • Thermodynamics
  • Potentiometry
  • Molecular Mimicry
  • Molecular Conformation
  • Metalloporphyrins
  • General Chemistry
  • Electrochemistry
  • 03 Chemical Sciences
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Fletcher, J. T., & Therien, M. J. (2002). Extreme electronic modulation of the cofacial porphyrin structural motif. Journal of the American Chemical Society, 124(16), 4298–4311. https://doi.org/10.1021/ja012489h
Fletcher, James T., and Michael J. Therien. “Extreme electronic modulation of the cofacial porphyrin structural motif.Journal of the American Chemical Society 124, no. 16 (April 2002): 4298–4311. https://doi.org/10.1021/ja012489h.
Fletcher JT, Therien MJ. Extreme electronic modulation of the cofacial porphyrin structural motif. Journal of the American Chemical Society. 2002 Apr;124(16):4298–311.
Fletcher, James T., and Michael J. Therien. “Extreme electronic modulation of the cofacial porphyrin structural motif.Journal of the American Chemical Society, vol. 124, no. 16, Apr. 2002, pp. 4298–311. Epmc, doi:10.1021/ja012489h.
Fletcher JT, Therien MJ. Extreme electronic modulation of the cofacial porphyrin structural motif. Journal of the American Chemical Society. 2002 Apr;124(16):4298–4311.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

April 2002

Volume

124

Issue

16

Start / End Page

4298 / 4311

Related Subject Headings

  • Thermodynamics
  • Potentiometry
  • Molecular Mimicry
  • Molecular Conformation
  • Metalloporphyrins
  • General Chemistry
  • Electrochemistry
  • 03 Chemical Sciences