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Issue 1, 2016
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A flexible iron(II) complex in which zero-field splitting is resistant to structural variation

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Abstract

The relationship between electronic structure and zero-field splitting dictates key design parameters for magnetic molecules. In particular, to enable the directed synthesis of new electronic spin based qubits, developing complexes where zero-field splitting energies are invariant to structural changes is a critical challenge. Toward those ends, we report three salts of a new compound, a four-coordinate iron(II) complex [Fe(C3S5)2]2− ([(18-crown-6)K]+ (1), Ph4P+ (2), Bu4N+ (3)) with a continuous structural variation in a single parameter, the dihedral angle (θd) between the two C3S52− ligands, as a function of counterion (θd = 89.98(4)° for 1 to 72.41(2)° for 3). Electron paramagnetic resonance data for 1–3 reveal zero-field splitting parameters that are unusually robust to the structural variation. Mössbauer spectroscopic measurements indicate that the structural variation in θd primarily affects the highest-energy 3d-orbitals (dxz and dyz) of the iron(II) ion. These orbitals have the smallest impact on the zero-field splitting parameters, thus the distortion has a minor effect on D and E. These results represent the first part of a directed effort to understand how spin state energies may be fortified against structural distortions for future applications of qubits in non-crystalline environments.

Graphical abstract: A flexible iron(ii) complex in which zero-field splitting is resistant to structural variation

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Publication details

The article was received on 09 Jul 2015, accepted on 02 Oct 2015 and first published on 19 Oct 2015


Article type: Edge Article
DOI: 10.1039/C5SC02477C
Citation: Chem. Sci., 2016,7, 416-423
  • Open access: Creative Commons BY-NC license
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    A flexible iron(II) complex in which zero-field splitting is resistant to structural variation

    J. M. Zadrozny, S. M. Greer, S. Hill and D. E. Freedman, Chem. Sci., 2016, 7, 416
    DOI: 10.1039/C5SC02477C

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