Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties: Redox control by metal cation complexation and anion binding

Nathan L. Bill, Masatoshi Ishida, Steffen Bähring, Jong Min Lim, Sangsu Lee, Christina M. Davis, Vincent M. Lynch, Kent A. Nielsen, Jan O. Jeppesen, Kei Ohkubo, Shunichi Fukuzumi, Dongho Kim, Jonathan L. Sessler

Research output: Contribution to journalArticle

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Abstract

A new class of redox-active free base and metalloporphyrins fused with the 1,3-dithiol-2-ylidene subunits present in tetrathiafulvalene, termed MTTFP (M = H2, Cu, Ni, Zn), have been prepared and characterized. The strong electron-donating properties of MTTFP were probed by electrochemical measurement and demonstrated that oxidation potentials can be tuned by metalation of the free base form, H2TTFP. X-ray crystal structures of H 2TTFP, ZnTTFP, and CuTTFP revealed that a severe saddle-shape distortion was observed with the dithiole rings bent out of the plane toward one another in the neutral form. In contrast, the structure of the two-electron oxidized species (CuTFFP2+) is planar, corresponding to a change from a nonaromatic to aromatic structure upon oxidation. A relatively large two-photon absorption (TPA) cross-section value of H2TTFP 2+ (1200 GM) was obtained for the free base compound, a value that is much higher than those typically seen for porphyrins (<100 GM). Augmented TPA values for the metal complexes were also seen. The strong electron-donating ability of ZnTTFP was further enhanced by binding of Cl- and Br - as revealed by thermal electron-transfer between ZnTTFP and Li +-encapsulated C60 (Li+@C60) in benzonitrile, which was "switched on" by the addition of either Cl- or Br- (as the tetrabutylammonium salts). The X-ray crystal structure of Cl--bound ZnTTFP was determined and provided support for the strong binding between the Cl- anion and the Zn 2+ cation present in ZnTTFP.

Original languageEnglish
Pages (from-to)10852-10862
Number of pages11
JournalJournal of the American Chemical Society
Volume135
Issue number29
DOIs
Publication statusPublished - Jul 24 2013

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Porphyrins
Complexation
Oxidation-Reduction
Anions
Cations
Negative ions
Positive ions
Metals
Electrons
Photons
Crystal structure
X-Rays
Metalloporphyrins
X rays
Oxidation
Coordination Complexes
Metal complexes
Salts
Hot Temperature
dithiol

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties : Redox control by metal cation complexation and anion binding. / Bill, Nathan L.; Ishida, Masatoshi; Bähring, Steffen; Lim, Jong Min; Lee, Sangsu; Davis, Christina M.; Lynch, Vincent M.; Nielsen, Kent A.; Jeppesen, Jan O.; Ohkubo, Kei; Fukuzumi, Shunichi; Kim, Dongho; Sessler, Jonathan L.

In: Journal of the American Chemical Society, Vol. 135, No. 29, 24.07.2013, p. 10852-10862.

Research output: Contribution to journalArticle

Bill, NL, Ishida, M, Bähring, S, Lim, JM, Lee, S, Davis, CM, Lynch, VM, Nielsen, KA, Jeppesen, JO, Ohkubo, K, Fukuzumi, S, Kim, D & Sessler, JL 2013, 'Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties: Redox control by metal cation complexation and anion binding', Journal of the American Chemical Society, vol. 135, no. 29, pp. 10852-10862. https://doi.org/10.1021/ja404830y
Bill, Nathan L. ; Ishida, Masatoshi ; Bähring, Steffen ; Lim, Jong Min ; Lee, Sangsu ; Davis, Christina M. ; Lynch, Vincent M. ; Nielsen, Kent A. ; Jeppesen, Jan O. ; Ohkubo, Kei ; Fukuzumi, Shunichi ; Kim, Dongho ; Sessler, Jonathan L. / Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties : Redox control by metal cation complexation and anion binding. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 29. pp. 10852-10862.
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abstract = "A new class of redox-active free base and metalloporphyrins fused with the 1,3-dithiol-2-ylidene subunits present in tetrathiafulvalene, termed MTTFP (M = H2, Cu, Ni, Zn), have been prepared and characterized. The strong electron-donating properties of MTTFP were probed by electrochemical measurement and demonstrated that oxidation potentials can be tuned by metalation of the free base form, H2TTFP. X-ray crystal structures of H 2TTFP, ZnTTFP, and CuTTFP revealed that a severe saddle-shape distortion was observed with the dithiole rings bent out of the plane toward one another in the neutral form. In contrast, the structure of the two-electron oxidized species (CuTFFP2+) is planar, corresponding to a change from a nonaromatic to aromatic structure upon oxidation. A relatively large two-photon absorption (TPA) cross-section value of H2TTFP 2+ (1200 GM) was obtained for the free base compound, a value that is much higher than those typically seen for porphyrins (<100 GM). Augmented TPA values for the metal complexes were also seen. The strong electron-donating ability of ZnTTFP was further enhanced by binding of Cl- and Br - as revealed by thermal electron-transfer between ZnTTFP and Li +-encapsulated C60 (Li+@C60) in benzonitrile, which was {"}switched on{"} by the addition of either Cl- or Br- (as the tetrabutylammonium salts). The X-ray crystal structure of Cl--bound ZnTTFP was determined and provided support for the strong binding between the Cl- anion and the Zn 2+ cation present in ZnTTFP.",
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T1 - Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties

T2 - Redox control by metal cation complexation and anion binding

AU - Bill, Nathan L.

AU - Ishida, Masatoshi

AU - Bähring, Steffen

AU - Lim, Jong Min

AU - Lee, Sangsu

AU - Davis, Christina M.

AU - Lynch, Vincent M.

AU - Nielsen, Kent A.

AU - Jeppesen, Jan O.

AU - Ohkubo, Kei

AU - Fukuzumi, Shunichi

AU - Kim, Dongho

AU - Sessler, Jonathan L.

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N2 - A new class of redox-active free base and metalloporphyrins fused with the 1,3-dithiol-2-ylidene subunits present in tetrathiafulvalene, termed MTTFP (M = H2, Cu, Ni, Zn), have been prepared and characterized. The strong electron-donating properties of MTTFP were probed by electrochemical measurement and demonstrated that oxidation potentials can be tuned by metalation of the free base form, H2TTFP. X-ray crystal structures of H 2TTFP, ZnTTFP, and CuTTFP revealed that a severe saddle-shape distortion was observed with the dithiole rings bent out of the plane toward one another in the neutral form. In contrast, the structure of the two-electron oxidized species (CuTFFP2+) is planar, corresponding to a change from a nonaromatic to aromatic structure upon oxidation. A relatively large two-photon absorption (TPA) cross-section value of H2TTFP 2+ (1200 GM) was obtained for the free base compound, a value that is much higher than those typically seen for porphyrins (<100 GM). Augmented TPA values for the metal complexes were also seen. The strong electron-donating ability of ZnTTFP was further enhanced by binding of Cl- and Br - as revealed by thermal electron-transfer between ZnTTFP and Li +-encapsulated C60 (Li+@C60) in benzonitrile, which was "switched on" by the addition of either Cl- or Br- (as the tetrabutylammonium salts). The X-ray crystal structure of Cl--bound ZnTTFP was determined and provided support for the strong binding between the Cl- anion and the Zn 2+ cation present in ZnTTFP.

AB - A new class of redox-active free base and metalloporphyrins fused with the 1,3-dithiol-2-ylidene subunits present in tetrathiafulvalene, termed MTTFP (M = H2, Cu, Ni, Zn), have been prepared and characterized. The strong electron-donating properties of MTTFP were probed by electrochemical measurement and demonstrated that oxidation potentials can be tuned by metalation of the free base form, H2TTFP. X-ray crystal structures of H 2TTFP, ZnTTFP, and CuTTFP revealed that a severe saddle-shape distortion was observed with the dithiole rings bent out of the plane toward one another in the neutral form. In contrast, the structure of the two-electron oxidized species (CuTFFP2+) is planar, corresponding to a change from a nonaromatic to aromatic structure upon oxidation. A relatively large two-photon absorption (TPA) cross-section value of H2TTFP 2+ (1200 GM) was obtained for the free base compound, a value that is much higher than those typically seen for porphyrins (<100 GM). Augmented TPA values for the metal complexes were also seen. The strong electron-donating ability of ZnTTFP was further enhanced by binding of Cl- and Br - as revealed by thermal electron-transfer between ZnTTFP and Li +-encapsulated C60 (Li+@C60) in benzonitrile, which was "switched on" by the addition of either Cl- or Br- (as the tetrabutylammonium salts). The X-ray crystal structure of Cl--bound ZnTTFP was determined and provided support for the strong binding between the Cl- anion and the Zn 2+ cation present in ZnTTFP.

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