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Spinning Molecules, Spinning Spins: Modulation of an Electron Spin Exchange Interaction in a Highly Anisotropic Hyperfine Field.
- Source :
-
ACS omega [ACS Omega] 2021 Oct 18; Vol. 6 (42), pp. 27865-27873. Date of Electronic Publication: 2021 Oct 18 (Print Publication: 2021). - Publication Year :
- 2021
-
Abstract
- 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 <subscript>avg</subscript> ) between the Cu centers. In this work, an additional line broadening parameter ( J <subscript>mod</subscript> ) is explored in detail via variable temperature X-band EPR in liquid solution for several different structures. The J <subscript>mod</subscript> phenomenon is due to fluctuations in the spin exchange interaction caused by conformational motion of the porphyrin planes. The J <subscript>mod</subscript> 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 <subscript>mod</subscript> analysis within a highly anisotropic hyperfine field and demonstrates the utility of the theory for extraction of dynamic information.<br />Competing Interests: The authors declare no competing financial interest.<br /> (© 2021 The Authors. Published by American Chemical Society.)
Details
- Language :
- English
- ISSN :
- 2470-1343
- Volume :
- 6
- Issue :
- 42
- Database :
- MEDLINE
- Journal :
- ACS omega
- Publication Type :
- Academic Journal
- Accession number :
- 34722986
- Full Text :
- https://doi.org/10.1021/acsomega.1c03490