Supramolecular dimers are the simplest unit of assembly for building up intermolecular architectures. The desired properties leading to modular supramolecular dimerization are versatile building blocks and reliable intermolecular linkage chemistries. Anion-anion dimerization is reliable when taking place inside dimers of cyanostar macrocycles. Therein, hydroxyanions like alkyl-phosphonates, alkyl-phosphates and aryl-phosphates are held together by anti-electrostatic hydrogen bonding but the organic substituents require tailored synthesis each and every time. Herein, we explore vinyl phosphonates as versatile and modular building blocks for driving anion dimerization inside cyanostar macrocycles using 10 different substituents. All form discrete and reliable 2:2 macrocycle:anion linkages in dichloromethane solution. The 2:2 stoichiometries were verified by characteristic 1H-NMR signals for macrocycle dimers in the aromatic region and the anti-electrostatic hydrogen bonds between anions at around 14 ppm and supported by an X-ray crystal structure. Use of ditopic vinyl phosphonates provided direct access to anion-driven supramolecular polymers where the modularity was critical for tuning solubility. Given the modular synthesis of vinyl phosphonates from commercial resources, the assembly of these novel vinyl phosphonates pave the way to study anion-driven assembly of hydroxyanions and cyanostar in the absence of other intermediates.

Versatile and modular anion-anion dimers of vinyl phosphonates with cyanostars and their supramolecular polymers

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