Postassembly Modification of Interior Spaces Within M ₁₂ L ₂₄ Nanospheres

Abstract

Abstract Post assembly modification (PAM) of coordination‐based supramolecular self‐assemblies has developed in the past 10 years as a tool that allows expansion of the chemical diversity available in supramolecular synthesis. In this contribution we apply PAM to enable the creation of M 12 L 24 nanospheres with unique interior spaces. We introduce alkyl N ‐pyridinium carboxy aldehydes (ANCA) as ideal orthogonal functional group for PAM. The herein presented nanospheres undergo quantitative PAM with a variety of aniline derivatives, allowing the creation of hydrophobic, chiral, catalytic, and other confined spaces. As the parent spheres can be easily characterized before PAM, this methodology not only allows for the preparation of highly desirable multifunctional confined spaces but also serves with its post modulation possibilities as a fast and efficient tool for screening secondary interactions and confined spaces on probes of interest.