Self‐Assembly and Characterization of 3D Metallamacrocycles: A Study of Supramolecular Constitutional Isomers

We report the self-assembly and isolation of two metallamacromolecular constitutional isomeric pairs based on < tpy-MII-tpy > connectivity. Utilizing a robust < tpy-RuII-tpy > dimer with varying substitution to the core benzene ring resulted not only in the isolation of the expected 60 degrees-oriented tetramer and 120 degrees-oriented hexamer but also in the unexpected isolation of a 60 degrees-oriented hexamer and a 120 degrees-oriented tetramer. These isomers were characterized by 1H NMR spectroscopy and mass spectrometry (ESI-travelling wave ion mobility), which revealed significant structural differences. Molecular modeling was utilized to aid in characterization.