Altering the solubility of metal-organic polyhedra via pendant functionalization of Cp 3 Zr 3 O(OH) 3 nodes.
Meghan G SullivanGregory E SokolowEric T JensenMatthew R CrawleySamantha N MacMillanTimothy R CookPublished in: Dalton transactions (Cambridge, England : 2003) (2022)
The chemistry of zirconium-based metal-organic polyhedra (ZrMOPs) is often limited by their poor solubilities. Despite their attractive features-including high yielding and facile syntheses, predictable topologies, high stability, and tunability-problematic solubilities have caused ZrMOPs to be under-studied and under-applied. Although these cages have been synthesized with a wide variety of carboxylate-based bridging ligands, we explored a new method for ZrMOP functionalization via node-modification, which we hypothesized could influence solubility. Herein, we report ZrMOPs with benzyl-, vinylbenzyl-, and trifluoromethylbenzyl-pendant groups decorating cyclopentadienyl moieties. The series was characterized by 1 H/ 19 F NMR, high-resolution mass spectrometry, infrared spectroscopy, and single-crystal X-ray diffraction. The effects of node functionalities on ZrMOP solubility were quantified using inductively coupled plasma mass spectrometry. Substitution caused a decrease in water solubility, but for certain organic solvents, e.g. DMF, solubility could be enhanced by ∼20×, from 16 μM for the unfunctionalized cage to 310 μM for the vinylbenzyl- and trifluoromethylbenzyl-cages.
Keyphrases
- liquid chromatography
- high resolution mass spectrometry
- mass spectrometry
- high resolution
- water soluble
- lymph node
- gas chromatography
- solid state
- magnetic resonance
- magnetic resonance imaging
- high performance liquid chromatography
- squamous cell carcinoma
- quantum dots
- tandem mass spectrometry
- capillary electrophoresis
- ms ms
- computed tomography
- early stage
- radiation therapy
- highly efficient
- reduced graphene oxide
- simultaneous determination
- gold nanoparticles