Size-Selective Catalytic Polymer Acylation with a Molecular Tetrahedron

Abstract

We report an original catalytic molecular tetrahedron. By threading through the cavity of the tetrahedron, polymeric substrates are unfolded or broken apart. Our catalyst distinguishes between polymer chains of different lengths, functionalizing the shorter polymers selectively over the longer ones-as a proof of concept for selective catalysis to modify polymers. Our findings advance the fundamental understanding of the thermodynamic and kinetic phenomena controlling the interactions between molecular cages and synthetic polymers, offering valuable ability to create complex materials in the future.

New horizons for catalysis disclosed by supramolecular chemistry

“…13,63,64 Remarkably, even polymers can be modified in a site-selective manner following this approach. 65 Regio-selectivity can be modulated in a similar way. As an example, Ribas and coworkers recently applied this approach to accomplish a highly regio-selective poly-functionalization of fullerene (Fig.…”

“…171 Other outstanding examples of processive catalysts have been reported by Harada, 172 who coupled α-and β-cyclodextrins to polymerize δ-valerolactone, by Leigh who prepared a pseudo-rotaxane in which, during its oriented dethread along the axis, the wheel iteratively and sequentially acquires three aminoacids 173 (or four in a more recent development 174 ) to form a pendant peptidic chain, and lately by Li and Schneebeli who obtained the size-selective acylation of the amino groups present in the chains of polydisperse polymer mixtures by threading the polymer chains into hydrazone-based molecular tetrahedrons decorated with tryglime units. 65…”

Graph-based Automated Macro-Molecule Assembly

“…Particularly attractive design goals are molecular scaffolds for catalysis − as potentially more general and versatile alternatives to biological enzymes. As with enzymes, both steric features and electric fields are important considerations for the catalytically active site(s) (cf.…”

FeII4L4 tetrahedron binds and aggregates DNA G-quadruplexes

“…[16][17][18][19][20] Self-assembled metal-organic cages are useful for a range of applications including catalysis, biomedicine, molecular sensing, gas absorption and molecular separation. [21][22][23][24][25] Previous studies have shown that various metal organic assemblies can recognize the structure of DNA G4 and alter its conformation. [5][6][7][26][27][28][29][30] The structural tunability and encapsulation ability of coordination cages render them useful for biosensing, drug delivery and cancer therapy.…”