Dysprosium complexes with mono-/di-carboxylate ligands—From simple dimers to 2D and 3D frameworks

Four dysprosium (Dy) single carboxylates, a formate, a propionate, a butyrate and an oxalate have been synthesized and structurally characterized. The structure of Dy(HCO₂)₃ (1) contains nine-fold coordinated Dy polyhedra in perfect tricapped trigonal prisms. They are linked through trigonal O atoms forming 1D pillars which are further linked together through tricapped O atoms into a 3D pillared metal organic framework. The network structure is stable up to 360 °C. The structure of [Dy₂(C₂O₄)₃(H₂O)₆]·2.5H₂O (2) contains nine-fold coordinated Dy polyhedra linking together through μ₂-bridging oxalate anions into a 2D hexagonal layered structure. Both [Dy₂(Pr)₆(H₂O)₄]·(HPr)_0.5 (3) [Pr=(C₂H₅CO₂)⁻¹] and [Dy₂(Bu)₆(H₂O)₄] (4) [Bu=(C₃H₇CO₂)⁻¹] have similar di-nuclear structures. The Raman vibration modes of the complexes have been investigated. - Graphical abstract: Four dysprosium (Dy) complexes with formate, propionate, butyrate and oxalate ligands have been synthesized and characterized. The Dy formato complex has a 3D pillared metal organic framework and the structure is stable up to 360 °C whilst the complexes with longer alkyl chained mono-carboxylates possess similar di-nuclear structures. The Dy oxalato complex has a 2D hexagonal (honeycomb-type) structure. Their Raman vibration modes have been investigated. - Highlights: • New Dysprosium complexes with formate, propionate, butyrate and oxalate ligands. • Crystal structures range from dimers to two and three dimensional frameworks. • Vibrational modes have been investigated and correlated to the structures. • The complexes are thermal robust and stable to over 300 °C