A Scandium MOF with an Unprecedented Inorganic Building Unit, Delimiting the Micropore Windows.

A new scandium metal-organic framework (Sc-MOF) with the composition of [Sc(OH)(OBA)], denoted as Sc-CAU-21, was prepared under solvothermal reaction conditions using 4,4'-oxidibenzoic acid (H2OBA) as the ligand. Single-crystal structure determination revealed the presence of the new inorganic building unit (IBU) {Sc8(μ-OH)8(O2C)16}. It is composed of cis-connected ScO6 polyhedra forming an eight-membered ring through bridging μ-OH groups. The connection of the IBUs leads to a 3D framework, containing 1D pores with a diameter between 4.2 and 5.6 Å. Pore access is limited by the size of the IBU, and in contrast to the isoreticular aluminum compound Al-CAU-21 [Al(OH)(OBA)], which is nonporous toward nitrogen at 77 K, Sc-CAU-21 exhibits a specific surface area of 610 m2 g-1. The title compound is thermally stable in air up to 350 °C and can be employed as a host for photoluminescent ions. Sc-CAU-21 exhibits a ligand-based blue emission, and (co)substituting Sc3+ ions with Ln3+ ions (Eu3+, Tb3+, and Dy3+) allows the tuning of the emitting color of the phosphor from red to green. Single-phase white-light emission with CIE color coordinates close to the ideal for white-light emission was also achieved. The luminescence property was utilized in combination with powder X-ray diffraction to study in situ the crystallization process of Sc-CAU-21:Tb and Sc-CAU-21:Eu. Both studies indicate a two-step crystallization process, with a crystalline intermediate, prior to the formation of Sc-CAU-21:Ln.