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. Ion binding studies using the cuboctahedral cage were undertaken.

The self-assembly of the o-carborane-based, bisterpyridyl monomer, 1,2-bis[4'-(4-ethynylphenyl)-2,2':6',2''-terpyridine]-o-carborane, utilizing either Zn(II) or Fe(II) in a precise metal : ligand ratio (1 : 1), generated a family of metallomacrocycles that were studied via ESI-TWIM-MS, (1)H NMR, and 2D NMR (COSY, NOESY). Under kinetic control, via formation of Fe(II) complexes, the main cyclic product was triangular, as is typical of 60°-based bisligands. Under thermodynamic control using more labile transition metal complexes, e.g. Zn(II), the ratio of cyclic species was found to be concentration and temperature dependent, and under an adequate entropic driving force, the cyclic dimer was formed. This system was probed via variable temperature NMR to reveal dynamic equilibrium between the entropically favored dimer and enthalpically favored trimer.

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). The mobility separated ions are subsequently identified by their mass-to-charge-ratios and isotope patterns in the orthogonal MS dimension. Finally, the gMS(2) dimension reveals bond breaking proclivities and disintegration pathways of the assemblies. The described methodology does not require high sample purity due to the dispersive nature of the IM and MS steps. Its utility is demonstrated with the comprehensive analysis of bisterpyridine-based metallomacrocycle mixtures and a tristerpyridine based complex with 3-D nanosphere-like architecture.

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 (11.3 nm diameter), and its core was previously established. The series of complexes has been unequivocally characterized by NMR, ESI-IM-MS, and TEM techniques.

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.