RESUMEN
The reversible condensation of catechols and boronic acids to boronate esters is a paradigm reaction in dynamic covalent chemistry. However, facile backward hydrolysis is detrimental for stability and has so far prevented applications for boronate-based materials. Here, we introduce cubic boronate ester cages 6 derived from hexahydroxy tribenzotriquinacenes and phenylene diboronic acids with ortho-t-butyl substituents. Due to steric shielding, dynamic exchange at the Lewis acidic boron sites is feasible only under acid or base catalysis but fully prevented at neutral conditions. For the first time, boronate ester cages 6 tolerate substantial amounts of water or alcohols both in solution and solid state. The unprecedented applicability of these materials under ambient and aqueous conditions is showcased by efficient encapsulation and on-demand release of ß-carotene dyes and heterogeneous water oxidation catalysis after the encapsulation of ruthenium catalysts.
RESUMEN
Reliable structure elucidation of covalent organic cage compounds remains challenging as routine analysis might leave ambiguities. Diffusion-ordered NMR spectroscopy (DOSY) allows insight into the molecular size and mass of the species present in solution, but a systematic evaluation of the diffusion behavior for cage assemblies is rarely considered. Here we report the synthesis of four series of covalent organic cages based on tribenzotriquinacenes and diboronic acids with varying geometry and exohedral substituents. We provide a guideline for the consistent measurement of diffusion coefficients from 1 H-DOSYâ NMR spectroscopy, which was utilized to study the diffusion behavior for the whole set of cages and selected examples from the literature. For structurally similar cages, a linear correlation between the solvodynamic volume and the molecular mass allows precise size determination. For more complex systems, multiple parameters, such as window size or rigid exohedral functionalization. further modulate cage diffusion in solution.
