Controlled Interconversion of Superposed-Bistriangle, Octahedron, and Cuboctahedron Cages Constructed Using a Single, Terpyridinyl-Based Polyligand and Zn²⁺

Abstract

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.

Divergent Terpyridine‐Based Coordination for the Construction of Photoactive Supramolecular Structures

“…As a consequence of the high binding affinity, custom‐made terpyridine monomers combined with suitable metals give rise to programmable and highly ordered 2D and 3D structures . These supramolecular materials based on terpyridine‐containing p‐conjugated polymers found application in optoelectronic devices like organic light‐emitting diode, photovoltaic cells, organic field‐effect transistors and ion sensors , .…”

Stepwise Self‐Assembly and Dynamic Exchange of Supramolecular Nanocages Based on Terpridine Building Blocks

“…Numerous tpy‐based metallo‐supramolecules, including triangle, hexagons, fractals, spoked wheels, and nested concentric ring have been reported. Despite several elegant reports, the synthesis of tpy‐based 3D nanocages is still challenging in terms of diversity and complexity.…”

Collision cross‐section analysis of self‐assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry

“…25,41 Zn 2+ forms stronger coordinative bonds, 19,44 but still permits reversible interconversions. 26 In addition to cyclic dimers-tetramers, this metal cogenerated cyclic hexamers, which had been observed in low yield with other 60 o ligands 25 (a 120 o dihedral angle favors hexameric macrocycle formation 21,22 ). With Ni 2+ , which binds bis(terpyridine) ligands more strongly than Zn 2+ , 19,44 1 Average Ω exp values of all metals for each group of cyclic (C n ) and linear (L n ) species in Table 1; the numbers in parentheses are the corresponding standard deviations.…”

“…IM-MS has been instrumental in establishing the latter structural features with high sensitivity and specificity, especially when mixtures with isobars and isomers are generated that are difficult to characterize by other analytical techniques. 8,[21][22][23][24][25][26][27][28][29][30][31] An important attribute of IM-MS that sets it apart from other characterization techniques is its ability to separate isobaric and isomeric ions in the gas phase, which is often necessary for samples formed by coordination-driven self-assembly reactions. Electrospray ionization (ESI) is the method of choice for the mass spectrometry (MS) analysis of these samples, as most metal ligands contain highly conjugated UV chromophores that preclude the use of laserbased ionization.…”

“…10,13,35 In addition, the Ω values of individual architectures can be calculated using molecular modeling simulations 36 for comparison with the experimental results from IM-MS drift times, so that 3D structural assignments can be made confidently. 10,22,23,26,27,31,35 In the present study, ESI-MS and ESI-IM-MS are used to characterize a large set of self-assembled metallo-supramolecular species synthesized from a single bis (terpyridine) ligand, designed to favor macrocyclization, and four divalent transition metals (Zn 2+ , Ni 2+ , Cd 2+ , Fe 2+ ). The species probed span over m/z 750-2500 and have Ω values ranging from 600 to 2200 Å 2 depending on their charge and self-assembled architecture.…”