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Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions.

Publication ,  Journal Article
Wang, R; Brugh, AM; Rawson, J; Therien, MJ; Forbes, MDE
Published in: Journal of the American Chemical Society
July 2017

Spin and conformational dynamics in symmetric alkyne-bridged multi[copper(II) porphyrin] structures have been studied in toluene solution at variable temperature using steady-state electron paramagnetic resonance (EPR) spectroscopy. Comparison of the dimer EPR spectra to those of Cu porphyrin monomers shows evidence of an isotropic exchange interaction (Javg) in these biradicaloid structures, manifested by a significant line broadening in the dimer spectra. The extent line broadening depends on molecular structure and temperature, suggesting Javg is modulated by conformational dynamics that impact the torsional angle distribution between the porphyrin-porphyrin least-squares planes. Computational simulation of the experimental EPR spectra, using a developed algorithm for J modulation in flexible organic biradicals, supports this hypothesis. Comparison of ethyne and butadiyne alkyne bridges reveals remarkable sensitivity to orbital interactions between the spacer and the metal, reflected in measurements of Javg as a function of temperature. The results suggest orbital symmetry relationships may be more important than recognized in design of optimized molecular spintronic devices.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

July 2017

Volume

139

Issue

29

Start / End Page

9759 / 9762

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Wang, R., Brugh, A. M., Rawson, J., Therien, M. J., & Forbes, M. D. E. (2017). Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions. Journal of the American Chemical Society, 139(29), 9759–9762. https://doi.org/10.1021/jacs.7b03252
Wang, Ruobing, Alexander M. Brugh, Jeff Rawson, Michael J. Therien, and Malcolm D. E. Forbes. “Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions.Journal of the American Chemical Society 139, no. 29 (July 2017): 9759–62. https://doi.org/10.1021/jacs.7b03252.
Wang R, Brugh AM, Rawson J, Therien MJ, Forbes MDE. Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions. Journal of the American Chemical Society. 2017 Jul;139(29):9759–62.
Wang, Ruobing, et al. “Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions.Journal of the American Chemical Society, vol. 139, no. 29, July 2017, pp. 9759–62. Epmc, doi:10.1021/jacs.7b03252.
Wang R, Brugh AM, Rawson J, Therien MJ, Forbes MDE. Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions. Journal of the American Chemical Society. 2017 Jul;139(29):9759–9762.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

July 2017

Volume

139

Issue

29

Start / End Page

9759 / 9762

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences