Supercharged, Precise, Megametallodendrimers via a Single-Step, Quantitative, Assembly Process.

Synthesis of giant unimolecular dendrimers is challenging due, in part, to difficulties encountered at higher generations, in both convergent and divergent protocols because of the multistep construction/purification process. Herein, we report a hybrid synthetic procedure in which the core is constructed last. This quantitative assembly generated a metallodendrimer that is supercharged (120+), large (11.

Controlled Interconversion of Superposed-Bistriangle, Octahedron, and Cuboctahedron Cages Constructed Using a Single, Terpyridinyl-Based Polyligand and Zn(2.).

Metallomacromolecular architectural conversion is expanded by the characterization of three different structures. A quantitative, single-step, self-assembly of a shape-persistent monomer, containing a flexible crown ether moiety, gives an initial Archimedean-based cuboctahedron that has been unequivocally characterized by 1D and 2D NMR spectroscopy, mass spectrometry, and collision cross section analysis. Both dilution and exchange of counterions, transforms this cuboctahedron into two identical octahedrons, which upon further dilution convert into four, superposed, bistrianglar complexes; increasing the concentration reverses the process.

Characterization of Metallosupramolecular Polymers by Top-Down Multidimensional Mass Spectrometry Methods.

Top-down multidimensional mass spectrometry, interfacing electrospray ionization (ESI) with ion mobility mass spectrometry (IM-MS), and energy resolved (gradient) tandem mass spectrometry (gMS(2) ) are employed to characterize the stoichiometries, architectures, and intrinsic stabilities of coordinatively bound supramolecular polymers containing terpyridine functionalized ligands. As a soft ionization method, ESI prevents or minimizes unwanted assembly destruction. The IM dimension affords separation of the supramolecular ions by charge and collision cross-section (a function of size and shape).

Directed flexibility: self-assembly of a supramolecular tetrahedron.

Self-assembly of a tribenzo-27-crown-9 ether functionalized with six terpyridines generated (85%) an expanded tetrahedral structure comprised of four independent triangular surfaces interlinked by crown ether vertices.