Issue 46, 2024

A highly conducting tetrathiafulvalene-tetracarboxylate based dysprosium(iii) 2D metal–organic framework with single molecule magnet behaviour

Abstract

The synthesis and whole characterization by a multitechnique approach of an unprecedented dysprosium(III) 2D metal organic framework (MOF), involving the redox-active tetrathiafulvalene (TTF)-based linker TTF-tetracarboxylate (TTF-TC), are herein reported. The single-crystal X-ray structure, formulated as [Dy6(TTF-TC)5(H2O)22]·21H2O (1), reveals a complex 2D topology, with hexanuclear Dy6 clusters as secondary building units (SBUs) interconnected by five linkers, stacked almost parallel in each layer and eclipsed along the [111] direction, leading to the formation of 1D channels filled by water molecules. The mixed valence of the TTF units is confirmed by both bond distance analysis, Raman microscopy and diffuse reflectance spectroscopy, and further supported by band structure calculations, which also predict activated conductivity for this material. Thanks to efficient TTF stacking and partial oxidation, 1 shows semiconducting behavior, with, however, a record conductivity value of 1 mS cm−1 at room temperature, when compared to the previously reported TTF-based MOFs. Furthermore, temperature and magnetic field dependent ac (alternative current) magnetic susceptibility measurements demonstrate field induced slow relaxation of magnetization, accounting for two independent relaxation processes, with an energy barrier (Ueff/K) of around 12 K, typical for dysprosium carboxylate complexes. The herein reported 2D Dy-MOF provides a valuable master plan for coexistence of conducting π-TTF stacks and highly anisotropic DyIII SMM properties.

Graphical abstract: A highly conducting tetrathiafulvalene-tetracarboxylate based dysprosium(iii) 2D metal–organic framework with single molecule magnet behaviour

Supplementary files

Article information

Article type
Edge Article
Submitted
27 Aug 2024
Accepted
29 Oct 2024
First published
30 Oct 2024
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., 2024,15, 19247-19263

A highly conducting tetrathiafulvalene-tetracarboxylate based dysprosium(III) 2D metal–organic framework with single molecule magnet behaviour

F. Manna, M. Oggianu, P. Auban-Senzier, G. Novitchi, E. Canadell, M. L. Mercuri and N. Avarvari, Chem. Sci., 2024, 15, 19247 DOI: 10.1039/D4SC05763E

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