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Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear ZnIIFeIIIFeIIIFeIIIZnII Complex

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Atanasov,  Mihail
Research Group Atanasov, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences;

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Citation

Walleck, S., Atanasov, M., Schnack, J., Bill, E., Stammler, A., Bögge, H., et al. (2021). Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear ZnIIFeIIIFeIIIFeIIIZnII Complex. Chemistry – A European Journal, 27(61), 15240-15251. doi:10.1002/chem.202102572.


Cite as: http://hdl.handle.net/21.11116/0000-0009-78A6-5
Abstract
The first confacial pentaoctahedron comprised of transition metal ions namely ZnIIFeIIIAFeIIIBFeIIIAZnII has been synthesized by using a dinucleating nonadentate ligand. The face-sharing bridging mode enforces short ZnII⋅⋅⋅FeIIIA and FeIIIA⋅⋅⋅FeIIIB distances of 2.83 and 2.72 Å, respectively. Ab-initio CASSCF/NEVPT2 calculations provide significant negative zero-field splittings for FeIIIA and FeIIIB with |DA|>|DB| with the main component along the C3 axis. Hence, a spin-Hamiltonian comprised of anisotropic exchange, zero-field, and Zeeman term was employed. This allowed by following the boundary conditions from the theoretical results the simulation in a theory-guided parameter determination with Jxy=+0.37, Jz=−0.32, DA=−1.21, EA=−0.24, DB=−0.35, and EB=−0.01 cm−1 supported by simulations of high-field magnetic Mössbauer spectra recorded at 2 K. The weak but ferromagnetic FeIIIAFeIIIB interaction arises from the small bridging angle of 84.8° being at the switch from anti- to ferromagnetic for the face-sharing bridging mode.