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Keywords:

  • Supramolecular chemistry;
  • Self-assembly;
  • Metallacycles;
  • Macrocycles;
  • Constitutional isomers

Abstract

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°-oriented tetramer and 120°-oriented hexamer but also in the unexpected isolation of a 60°-oriented hexamer and a 120°-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.