Electronic, Structural and Functional Versatility in Tetrathiafulvalene-Lanthanide Metal-Organic Frameworks


Tetrathiafulvalene-lanthanide (TTF-Ln) metal-organic frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein a new family of isostructural TTF-Ln MOFs is reported, denoted as MUV-5(Ln) (Ln=Gd, Tb, Dy, Ho, Er), exhibiting semiconducting properties as a consequence of the short intermolecular S...S contacts established along the chain direction between partially oxidised TTF moieties. In addition, this family shows photoluminescence properties and single-molecule magnetic behaviour, finding near-infrared (NIR) photoluminescence in the Yb/Er derivative and slow relaxation of the magnetisation in the Dy and Er derivatives. As such properties are dependent on the electronic structure of the lanthanide ion, the immense structural, electronic and functional versatility of this class of materials is emphasised.






Castells-Gil, J; Manas-Valero, S; Vitorica-Yrezabal, IJ; Ananias, D; Rocha, J; Santiago, R; Bromley, ST; Baldovi, JJ; Coronado, E; Souto, M; Minguez Espallargas, G

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This work has been supported by the European Union (ERC-2016-CoG 724681-S-CAGE), by the Spanish MICINN (CTQ2017-89528-P and MAT2017-89993-R co-financed by FEDER) and by the project CICECO-Aveiro Institute of Materials (FCT Ref. UID/CTM/50011/2019) financed by FCT/MCTES. We also thank the Spanish government for the provision of a Maria de Maeztu project (MDM-2015-0538) and the Generalitat Valenciana (PROMETEO/2017/066). G.M.E., M.S. and S.M.V. thank MICINN for a Ramon y Cajal, Juan de la Cierva-Formacion and FPU fellowships, respectively. J.C.-G. thanks the Spanish MINECO for a FPI Scholarship (CTQ2014-59209-P). J.J.B. thanks the EU for a Marie Sklodowska-Curie Fellowship (H2020-MSCA-IF-2016-751047). We thank the Diamond Light Source (UK) for the synchrotron beamtime (MT17379). We thank Roger Sanchis for electrochemical measurements and Gloria Agusti and Jose M. Martinez-Agudo for magnetic measurements.

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