Extreme electronic modulation of the cofacial porphyrin structural motif

James T. Fletcher, Michael J. Therien

Research output: Contribution to journalArticle

70 Citations (Scopus)

Abstract

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)] (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″-tetra-phenylporphinato) 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 σ-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a β-to-β 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.

Original languageEnglish
Pages (from-to)4298-4311
Number of pages14
JournalJournal of the American Chemical Society
Volume124
Issue number16
DOIs
StatePublished - Apr 24 2002
Externally publishedYes

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Porphyrins
Zinc
Modulation
Oxidation-Reduction
Electron energy levels
Zinc Compounds
Metals
Electrochemistry
Structural Models
Cycloaddition Reaction
Palladium
Cycloaddition
Cobalt
Spectrum Analysis
Electrons
Topology

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Extreme electronic modulation of the cofacial porphyrin structural motif. / Fletcher, James T.; Therien, Michael J.

In: Journal of the American Chemical Society, Vol. 124, No. 16, 24.04.2002, p. 4298-4311.

Research output: Contribution to journalArticle

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abstract = "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)] (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″-tetra-phenylporphinato) 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 σ-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a β-to-β 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.",
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N2 - 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)] (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″-tetra-phenylporphinato) 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 σ-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a β-to-β 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.

AB - 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)] (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″-tetra-phenylporphinato) 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 σ-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a β-to-β 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.

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