Issue 1, 2016

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
09 Jul 2015
Accepted
02 Oct 2015
First published
19 Oct 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2016,7, 416-423

Author version available

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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