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 (d) between the two C3S52 ligands, as a function of counter ion (d = 89.98(4) for 1 to 72.41(2) for 3). Electron paramagnetic resonance data for 13 reveal zero-field splitting parameters that are unusually robust to the structural variation. Mssbauer spectroscopic measurements indicate that the structural variation in d 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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 19, 2015
- Accession Number
- AD1065082
Entities
People
- Danna E. Freedman
- Joseph M. Zadrozny
- Samuel M Greer
- Stephen Hill
Organizations
- Northwestern University