Spinning Molecules, Spinning Spins: Modulation of an Electron Spin Exchange Interaction in a Highly Anisotropic Hyperfine Field.

Journal Article (Journal Article)

An investigation of spin and conformational dynamics in a series of symmetric Cu-Cu porphyrin dimer solutions is presented using electron paramagnetic resonance (EPR) spectroscopy. Previous spectral simulations focused on the isotropic exchange interaction (J avg ) between the Cu centers. In this work, an additional line broadening parameter (J mod ) is explored in detail via variable temperature X-band EPR in liquid solution for several different structures. The J mod phenomenon is due to fluctuations in the spin exchange interaction caused by conformational motion of the porphyrin planes. The J mod parameter scales with the inverse of the rotational barriers that determine the Boltzmann-weighted torsional angle distribution between neighboring porphyrin planes. Arrhenius plots allow for extraction of the activation energies for rotation, which are 5.77, 2.84, and 5.31 kJ/mol for ethyne-bridged (porphinato)copper(II)-(porphinato)copper(II), butadiyne-bridged (porphinato)copper(II)-(porphinato)copper(II), and ethyne-bridged (porphinato)copper(II)-(porphinato)zinc(II)-(porphinato)copper(II) complexes, respectively. DFT calculations of these torsional barriers match well with the experimental results. This is the first report of a J mod analysis within a highly anisotropic hyperfine field and demonstrates the utility of the theory for extraction of dynamic information.

Full Text

Duke Authors

Cited Authors

  • Brugh, AM; Wang, R; Therien, MJ; Forbes, MDE

Published Date

  • October 2021

Published In

Volume / Issue

  • 6 / 42

Start / End Page

  • 27865 - 27873

PubMed ID

  • 34722986

Pubmed Central ID

  • PMC8552362

Electronic International Standard Serial Number (EISSN)

  • 2470-1343

International Standard Serial Number (ISSN)

  • 2470-1343

Digital Object Identifier (DOI)

  • 10.1021/acsomega.1c03490


  • eng