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Synthetic investigation of competing magnetic interactions in 2D metal–chloranilate radical frameworks

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Abstract

The discovery of emergent materials lies at the intersection of chemistry and condensed matter physics. Synthetic chemistry offers a pathway to create materials with the desired physical and electronic structures that support fundamentally new properties. Metal–organic frameworks are a promising platform for bottom-up chemical design of new materials, owing to their inherent chemical predictability and tunability relative to traditional solid-state materials. Herein, we describe the synthesis and magnetic characterization of a new 2,5-dihydroxy-1,4-benzoquinone based material, (NMe2H2)3.5Ga2(C6O4Cl2)3 (1), which features radical-based electronic spins on the sites of a kagomé lattice, a geometric lattice known to engender exotic electronic properties. Vibrational and electronic spectroscopies, in combination with magnetic susceptibility measurements, revealed 1 exhibits mixed valency between the radical-bearing trianionic and diamagnetic tetraanionic oxidation states of the ligand. This unpaired electron density on the ligand forms a partially occupied kagomé lattice where approximately 85% of the lattice sites are occupied with an S = ½ spin. We found that gallium mediates ferromagnetic coupling between ligand spins, creating a ferromagnetic kagomé lattice. By modulation of the interlayer spacing via post-synthetic cation metathesis of 1 to (NMe4)3.5Ga2(C6O4Cl2)3 (2) and (NEt4)2(NMe4)1.5Ga2(C6O4Cl2)3 (3), we determined the nature of the magnetic coupling between neighboring planes is antiferromagnetic. Additionally, we determined the role of the metal in mediating this magnetic coupling by comparison of 2 with the In3+ analogue, (NMe4)3.5In2(C6O4Cl2)3 (4), and we found that Ga3+ supports stronger superexchange coupling between ligand-based spins than In3+. The combination of intraplanar ferromagnetic coupling and interplanar antiferromagnetic coupling exchange interactions suggests these are promising materials to host topological phenomena.

Graphical abstract: Synthetic investigation of competing magnetic interactions in 2D metal–chloranilate radical frameworks

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Supplementary files

Article information


Submitted
08 Apr 2020
Accepted
10 May 2020
First published
11 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Synthetic investigation of competing magnetic interactions in 2D metal–chloranilate radical frameworks

K. A. Collins, R. J. Saballos, M. S. Fataftah, D. Puggioni, J. M. Rondinelli and D. E. Freedman, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC01994A

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