Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, c/ Catedrático José Beltrán 2, 46980, Paterna, Spain.
School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Chemistry. 2019 Sep 25;25(54):12636-12643. doi: 10.1002/chem.201902855. Epub 2019 Sep 5.
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.
四硫富瓦烯-镧系金属-有机骨架（TTF-Ln MOFs）是一类有趣的多功能材料，其中可以将多孔性与电子性质（如导电性、氧化还原活性、发光和磁性）相结合。本文报道了一类新的同构 TTF-Ln MOFs，记为 MUV-5（Ln）（Ln=Gd、Tb、Dy、Ho、Er），由于部分氧化的 TTF 部分之间沿链方向建立的短分子间 S⋅⋅⋅S 接触，表现出半导体性质。此外，该系列还表现出光致发光和单分子磁性行为，在 Yb/Er 衍生物中发现近红外（NIR）光致发光，在 Dy 和 Er 衍生物中发现磁化缓慢弛豫。由于这些性质取决于镧系离子的电子结构，因此强调了这类材料具有巨大的结构、电子和功能多样性。
