Uranyl phosphonates: crystalline materials and nanosheets for temperature sensing

Abstract

Ultrathin nanosheets of luminescent metal–organic frameworks or coordination polymers have been widely used for sensing ions, solvents and biomolecules but, as far as we are aware, not yet used for temperature sensing. Herein we report two luminescent uranyl phosphonates based on 2-(phosphonomethyl)benzoic acid (2-pmbH₃), namely (UO₂)(2-pmbH₂)₂ (1) and (H₃O)[(UO₂)₂(2-pmb)(2-pmbH)] (2). The former has a supramolecular layer structure, composed of chains of corner-sharing {UO₆} octahedra and {PO₃C} tetrahedra which are connected by hydrogen bonds between phosphonate and carboxylic groups. Compound 2 possesses a unique 2D anionic framework structure, where the inorganic uranyl phosphonate chains made up of {UO₇} and {PO₃C} polyhedra are cross-linked by 2-pmb³⁻ ligands. The carboxylic groups of 2-pmbH²⁻ ligands are pendant on the two sides of the layers and form hydrogen bonds between the layers. Both compounds can be exfoliated in acetone via a top-down freeze–thaw method, resulting in nanosheets of two-layer thickness. Interestingly, the photoluminescence (PL) of 1 and 2 is highly temperature sensitive. Variable temperature PL studies revealed that compounds 1 and 2 can be used as thermometers in the temperature ranges 120–300 K and 100–280 K, respectively. By doping the nanosheets into polymer matrix, 1-ns@PMMA and 2-ns@PMMA were prepared. The PL intensity of 1-ns@PMMA is insensitive to temperature, unlike that of the bulk sample. While 2-ns@PMMA exhibits similar temperature-dependent luminescence behaviour to its bulk counterpart, thereby enabling its potential application as a thermometer in the temperature range 100–280 K.