Preparation of dichloro(2,4,6-tribromophenoxy)(1,2-diphenoxy)phosphorane and its nonoxidative chlorination reactions with alkyl and aryl phosphonates

Byrd, Houston; Bharara, Prakash C.; Sullens, Tyler A.; Harden, Jeremiah D.; Gray, Gary M.

doi:10.1016/s0020-1693(02)01045-9

Cited by 4 publications

(1 citation statement)

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“…PCl 5 is a well-known chlorinating reagent in synthetic organic chemistry and can readily react with alcohols to form alkyl chlorides via substitutive chlorination. Chlorination of aromatic alcohols (ArOH) has not been observed using PCl 5 or PCl 3 , typically instead forming substituted chlorophosphoranes (ArO) x PCl 5– x . , We utilize analogous chemistry to install phosphorus moieties onto the MOF linker, 2-hydroxyterephthalate (BDC-OH), in UiO-66-OH to generate UiO-66-OP as illustrated in Scheme . Solution-state 1 H NMR spectra were collected on MOFs digested in 1 M NaOH/D 2 O before and after reaction with PCl 5 (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Phosphorus-Functionalized Organic Linkers Promote Polysulfide Retention in MOF-Based Li–S Batteries

Baumann

Anayah

Thoi

2022

ACS Appl. Energy Mater.

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Metal–organic frameworks (MOFs) have been an area of intense research for their high porosity and synthetic tunability, which afford them controllable physical and chemical properties for various applications. In this study, we demonstrate that functionalized MOFs can be used to mitigate the so-called polysulfide shuttle effect in lithium–sulfur batteries, a promising next-generation energy storage device. UiO-66-OH, a zirconium-based MOF with 2-hydroxyterephthalic acid, was functionalized with a phosphorus chloride species that was subsequently used to tether polysulfides. In addition, a molecular chlorophosphorane was synthesized as a model system to elucidate the chemical reactivity of the phosphorus moiety. The functionalized MOFs were then used as a cathode additive in coin cell batteries to inhibit the dissolution of polysulfides in solution. Through this work, we show that the functionalization of MOF with phosphorus enhances polysulfide redox and thereby capacity retention in Li–S batteries. While demonstrated here for polysulfide tethering in batteries, we envision this linker functionalization strategy could be more broadly utilized in separations, sensing, or catalysis applications.

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Section: Resultsmentioning

confidence: 99%