The Importance of Electronic Dimensionality in Multiorbital Radical Conductors
Mailman, A., Robertson, C. M., Winter, S. M., Dube, P. A., & Oakley, R. T. (2019). The Importance of Electronic Dimensionality in Multiorbital Radical Conductors. Inorganic Chemistry, 58(9), 6495-6506. https://doi.org/10.1021/acs.inorgchem.9b00691
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Inorganic ChemistryAuthors
Date
2019Copyright
© 2019 American Chemical Society
The exceptional performance of oxobenzene-bridged bis-1,2,3-dithiazolyls 6 as single-component neutral radical conductors arises from the presence of a low-lying π-lowest unoccupied molecular orbital, which reduces the potential barrier to charge transport and increases the kinetic stabilization energy of the metallic state. As part of ongoing efforts to modify the solid-state structures and transport properties of these so-called multiorbital materials, we report the preparation and characterization of the acetoxy, methoxy, and thiomethyl derivatives 6 (R = OAc, OMe, SMe). The crystal structures are based on ribbonlike arrays of radicals laced together by S···N′ and S···O′ secondary bonding interactions. The steric and electronic effects of the exocyclic ligands varies, affording one-dimensional (1D) π-stacked radicals for R = OAc, 1D cofacial dimer π-stacks for R = SMe, and a pseudo two-dimensional (2D) brick-wall arrangement for R = OMe. Variable-temperature magnetic and conductivity measurements reveal strong antiferromagnetic interactions and Mott insulating behavior for the two radical-based structures (R = OAc, OMe), with lower room-temperature conductivities (σRT ≈ 1 × 10–4 and ∼1 × 10–3 S cm–1, respectively) and higher thermal activation energies (Eact = 0.24 and 0.21 eV, respectively) than found for the ideal 2D brick-wall structure of 6 (R = F), where σRT ≈ 1 × 10–2 S cm–1 and Eact = 0.10 eV. The performance of R = OMe, OAc relative to that of R = F, is consistent with the results of density functional theory band electronic structure calculations, which indicate a lower kinetic stabilization energy of the putative metallic state arising from their reduced electronic dimensionality.
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European Commission; Academy of FinlandFunding program(s)
Academy Project, AoF

The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
Additional information about funding
This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERCC), the Univ. of Jyväskylä, the Academy of Finland (Project Nos. 253907 and 289172), and the European Union’s H2020 research and innovations programme (under the Marie Skłodowska-Curie Grant No. 659123). A.M. is grateful for the interest and support of Prof. H. M. Tuononen during this research. We also thank the Diamond Light Source for access to beamline I19.

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