It has been recognized for decades that the construction of high molecular weight compounds with well defined structures would benefit from the use of tools other than the reactions of covalent synthesis. Supramolecular chemistry has been developed as a powerful tool to access structures such as metal ion coordination based polygons and polyhedra. Unfortunately, the same reaction reversibility that allows efficient formation of self-assembled products also make them fragile and prevents chromatographic separation. Covalent stabilization is a process in which weak coordination N?Pt+ bonds are replaced with sturdy covalent C-Pt bonds, yielding products that can be chromatographed. The desired structures are thus obtained in two steps: self-assembly under thermodynamic control establishes the topology and covalent stabilization which renders the structure kinetically stable, keeps the topology intact. Covalent stabilization can be performed on a mixture of self-assembled structures that are equilibrated and inseparable, and the resulting covalent products are then separable. The procedure is exemplified on an exchange of doubly pyridine-terminated rods with doubly ethynyl-terminated rods under CuI/Et2NH catalysis. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/239nm/uploads/5144__figure1_.jpg' alt='' />

Covalent stabilization: A new tool in the chemist's toolkit

242nd National Meeting (2011)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.