Nanostructured Supramolecular Polymers with Allosterically Regulated Catalytic Interstices

Natural systems represent a source of inspiration when it comes to the processing of energy and matter.

Metalloporphyrins are at the core of many of these processes, harvesting solar energy and catalyzing relevant chemical processes.

In contrast to most artificial nanostructured catalysts based on porphyrins, in which the main assembly driving force is π-π stacking or metal-ligand coordination, enzymes teach us that the catalytic sites around the porphyrin metal centers must remain accessible to the relevant substrates (to optimize catalytic performance), embedded in a well-defined compartment (to enhance selectivity), and connected through the protein backbone (to allow for allosteric regulation).In SuprAlloCat we plan to apply some of the lessons learned from nature to target the self-assembly of nanostructured supramolecular polymers with catalytic performance that would combine the broad catalytic scope of homogeneous catalysts, and the allosteric control, selectivity and activity under mild conditions of enzymes.

The key to achieve such goal relies on the development of a self-assembly strategy that will allow us to cofacially arrange metalloporphyrins at tailored interstitial distances along a single dimension, thus creating a periodic array of connected nanoreactors with well-defined, accessible catalytic compartments.

The MSC candidate, Dr.

Alberto de Juan, will focus on the synthesis of porphyrin and ligand molecules equipped with complementary H-bonding units, and will proceed to study their combined assembly into 1D polymers.

We will then focus on evaluating unique functions in these supramolecular materials, such as host-guest binding, chiral induction, allosteric regulation and, finally, Lewis-acid catalysis.

SuprAlloCat introduces fundamental challenges and unprecedented approaches in chemical self-assembly and constitutes the best research scenario for the candidate to learn from different fields and further develop his scientific career.