Altering the solubility of metal-organic polyhedra pendant functionalization of CpZrO(OH) nodes

• Published in: Dalton transactions : an international journal of inorganic chemistry 2023-01, Vol.52 (2), p.338-346
• Main Authors: Sullivan, Meghan G, Sokolow, Gregory E, Jensen, Eric T, Crawley, Matthew R, MacMillan, Samantha N, Cook, Timothy R
• Format: Article
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d2dt03401h

The chemistry of zirconium-based metal-organic polyhedra ( ZrMOP s) 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 ZrMOP s 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 ZrMOP s 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. A new method to tune solubility of ZrMOP s via node-modification.