Developing novel lanthanide metal-organic frameworks (Ln-MOFs) to rapidly and reliably differentiate both metal ions in solution and volatile organic compounds (VOCs) in vapor is highly challenging. Here, we describe versatile Eu3+/Tb3+-MOFs based on a flexible ligand. It is noteworthy that the film fabricated using bimetallic Eu0.47Tb0.63-MOF and polyvinyl alcohol could serve as an easy and convenient luminescent platform for distinguishing different metal ions and VOCs. The luminescent film exhibits notable fingerprint correlation between the metal ions/VOCs and the emission intensity ratio of Eu3+/Tb3+ ions in Ln-MOFs. As a result, the bimetallic Ln-MOFs show fast recognition of Fe3+ ion with a response time of <10 s, and can effectively probe styrene vapor within 4 min. Since the developed Ln-MOF film is stable and reliable, this work presents a promising strategy to explore luminescent platforms capable of effectively sensing different metal ions and VOCs.
Selective C–C bond cleavage under ambient conditions is a challenging chemical transformation that can be a valuable tool for organic syntheses and macromolecular disassembly. Herein, we show that base metal vanadium photocatalysts can harvest visible light to effect the chemoselective C–C bond cleavage of lignin model compounds under ambient conditions. Lignin, a major aromatic constituent of non-food biomass, is an inexpensive, accessible source of fine chemical feedstocks such as phenols and aryl ethers. However, existing lignin degradation technologies are harsh and indiscriminately degrade valuable functional groups to produce intractable mixtures. The selective, photocatalytic depolymerization of lignin remains underexplored. In the course of our studies on lignin model compounds, we have uncovered a new C–C activation reaction that takes place under exceptionally mild conditions with high conversions. We present our fundamental studies on representative lignin model compounds, with the aim of expanding and generalizing the substrate scope in the future. Visible light is employed in the presence of earth-abundant vanadium oxo catalysts under ambient conditions. Selective C–C bond cleavage leads to valuable and functionally rich fine chemicals such as substituted aryl aldehydes and formates. Isotope labeling experiments, product analyses, and intermediate radical trapping, together with density functional theory studies, suggest a unique pathway that involves a photogenerated T1 state during the C–C bond cleavage reactions. Our study demonstrates a sustainable approach to harvest sunlight for an unusual, selective bond activation, which can potentially be applied in organic transformations and biomass valorization.
23 December 2016 in Journal of the American Chemical Society