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Keywords
NON-COVALENT SYNTHESIS, CHIRALITY, PORPHYRINS, CALIXARENES, CAVITANDS, HIERARCHICAL CONTROL

Hierarchical self-assembly of multicomponent supramolecular architectures

Università degli Studi di Catania
Abstract
The aim of this research project is the non-covalent synthesis of complex supramolecular systems employing a wide range of different building-blocks (porphirines, phtalocyanines, calixarenes, alkylammonium salts, bipiridine and phenantroline ruthenium complexes). The project focuses on the hierarchical self-assembly of “smart” supramolecular aggregates (chiral memory), resulting from electrostatic interactions between oppositely charged homo- and etero-components, and on the formation of nanostructured architectures (supramolecular polymers) harnessing intermolecular iterative host-guest inclusion events.
Some of the specific topics that we would like to investigate concern: the control of stoichiometry, tuning of the degree of aggregation/polymerization in response to chemical stimuli, automated microbatch crystallization, structural characterization of intermediates and final products both in solution and in solid state, separation/segregation of ion pairs, control of the stereochemistry, and induction/amplification of chirality.

Principal Investigator
Roberto Purrello Università degli Studi di CATANIA
Research Objectives
The main goal of this research proposal is the design, synthesis and characterization, both in solution and in the solid state, of homo-molecular (porphyrins:porphyrins and calixarenes:calixarenes) and hetero-molecular (calixarenes:porphyrins) aggregates. The hierarchical self-assembly, control of stoichiometry, tuning of the degree of aggregation/polymerization in response to chemical stimuli, automated microbatch crystallization, ion pair separation/confinement, steric and electronic complementarity, control of the stereochemistry, and induction/amplification of chirality are the specific topics that we will investigate.
Collaboration between the Units of Catania, Messina and Trieste stems not only from sharing common research interests, but also from a complementarity of instrumental and synthetic expertise that, owing to a methodological synergy, will allow us to design, prepare, characterize and study novel supramolecular entities. Two different approaches will be employed: classical covalent and non-covalent synthesis. The latter, in fact, is approaching the level of efficiency of traditional covalent-bond chemistry, and it “collaborates” with it for the rational design of suitable building blocks that are able to determine the specific properties of the supramolecular species.
The three Units will collaborate towards the synthesis of:
1) chiral porphyrin complexes;
2) self-assembled calixarene species.

Self-assembled chiral >>>

Timescale
24 months
National and international background
Molecular recognition is one of the most elegant and specific driven forces that Nature has selected for life machinery to work. The specificity of bio-recognition and bio-organization processes is ruled by (essentially electrostatic) non-covalent interactions and it is based on a remarkable degree of complementarity between the interacting species. This matching involves not only the dimension and shape of the molecular species but also their charge distribution. Non-covalent interactions play a central role in relevant biological processes as the central dogma of molecular genetics (replication?trascriptione?traslation), signal trasduction, selective transport across membranes of metal ions and small ligands, enzymatic reactions or aggregates formation. The high degree of specificity involved in the above processes clearly indicates that molecular complementarity deals not only with dimension and morphology of the interacting species but also with charge distribution. Supramolecular chemistry or, as defined by J. –M. Lehn (1), the chemistry “beyond the molecule” has exploited these principles, underlying that molecular recognition processes are not only intriguing to study per se, but also that they can become a methodological way to design species with well-defined physicochemical properties. In particular, many studies have been devoted to the non-covalent syntheses of supramolecular assemblies driven by self-assembly processes mediated by “weak-bonds” as: van der Waals >>>