Metal-Directed Self-Assembly of a Polyoxometalate-Based Molecular Triangle: Using Powerful Analytical Tools to Probe the Chemical Structure of Complex Supramolecular Assemblies.

Abstract

A polyoxometalate-based molecular triangle has been synthesized through the metal-driven self-assembly of covalent organic/inorganic hybrid oxo-clusters with remote pyridyl binding sites. The new metallomacrocycle was unambiguously characterized by using a combination of (1)H NMR spectroscopy, 2D diffusion NMR spectroscopy (DOSY), electrospray ionization travelling wave ion mobility mass spectrometry (ESI-TWIM-MS), small-angle X-ray scattering (SAXS) and molecular modelling. The collision cross-sections obtained from TWIM-MS and the hydrodynamic radii derived from DOSY are in good agreement with the geometry-optimized structures obtained by using theoretical calculations. Furthermore, SAXS was successfully employed and proved to be a powerful technique for characterizing such large supramolecular assemblies.