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Our group works in the field of Supramolecular Chemistry and is currently focused on three main topics:
Our group works in the field of Supramolecular Chemistry and is currently focused on three main topics:
There is an increasing interest in the temporal control of chemical systems that is often associated to the investigation on non-equilibrium chemical networks. We have exploited the special reactivity of activated carboxylic acids (ACAs) towards the decarboxylation, to drive the operation of a series of dissipative systems based one the acid-base reaction, which can be mantained in a protonated state in a time-controlled fashion. The ACA is added once, at the beginning of the operational cycle, and the system does anything by itself in a fire-and-forget modality following the program settled by the experimenter. The larger the amount of added ACA, the longer the time needed for its dissipation, the longer the time spent by the system in the protonated state. This way a number of ACA-based dissipative systems have been developed ranging from molecular machines to host-guest couples, from dynamic libraries to smart materials and supramolecular polymers. Such time-controlled systems operate under dissipative conditions or as energy ratchets.
There is an increasing interest in the temporal control of chemical systems that is often associated to the investigation on non-equilibrium chemical networks. We have exploited the special reactivity of activated carboxylic acids (ACAs) towards the decarboxylation, to drive the operation of a series of dissipative systems based one the acid-base reaction, which can be mantained in a protonated state in a time-controlled fashion. The ACA is added once, at the beginning of the operational cycle, and the system does anything by itself in a fire-and-forget modality following the program settled by the experimenter. The larger the amount of added ACA, the longer the time needed for its dissipation, the longer the time spent by the system in the protonated state. This way a number of ACA-based dissipative systems have been developed ranging from molecular machines to host-guest couples, from dynamic libraries to smart materials and supramolecular polymers. Such time-controlled systems operate under dissipative conditions or as energy ratchets.
Dynamic Combinatorial Chemistry and Macrocyclization Equilibria (go to selected publications on the topic)
Dynamic Combinatorial Chemistry and Macrocyclization Equilibria (go to selected publications on the topic)
The number of irreversible reactions used in the formation of synthetically useful covalent bonds largely outweighs that of reversible ones. Yet, the last period has witnessed a renewal of interest in the use of reversible reactions for synthetic purpose thanks to the birth of Dynamic Combinatorial Chemistry (DCC) mainly due to J.-M. Lehn, J. K. M. Sanders and S. Otto. In particular DCC has the potential to be a powerful tool for the synthesis of macrocyclic species under thermodynamic control because efficient cyclic receptors may be selected among a family of interconverting linear and cyclic members of a dynamic library (DL) upon the addition of a suitable template (T), via repeatedly occurring bond dissociation-recombination processes. Some reversible reactions such as acetal exchange, transimination and imine and olefin metathesis have been studied in our lab, in the frame of DCC. Furthermore, we are strongly interested in the physico-chemical laws governing the macrocyclization reactions that are very often at the basis of the systems studied in DCC. In the last period we have been working on a re-elaboration of the Jacobson-Stockmayer theory, which includes mechanical bonded species such as catenanes, into the classical treatment, and on experimental results proving our theories.
The number of irreversible reactions used in the formation of synthetically useful covalent bonds largely outweighs that of reversible ones. Yet, the last period has witnessed a renewal of interest in the use of reversible reactions for synthetic purpose thanks to the birth of Dynamic Combinatorial Chemistry (DCC) mainly due to J.-M. Lehn, J. K. M. Sanders and S. Otto. In particular DCC has the potential to be a powerful tool for the synthesis of macrocyclic species under thermodynamic control because efficient cyclic receptors may be selected among a family of interconverting linear and cyclic members of a dynamic library (DL) upon the addition of a suitable template (T), via repeatedly occurring bond dissociation-recombination processes. Some reversible reactions such as acetal exchange, transimination and imine and olefin metathesis have been studied in our lab, in the frame of DCC. Furthermore, we are strongly interested in the physico-chemical laws governing the macrocyclization reactions that are very often at the basis of the systems studied in DCC. In the last period we have been working on a re-elaboration of the Jacobson-Stockmayer theory, which includes mechanical bonded species such as catenanes, into the classical treatment, and on experimental results proving our theories.
Non-heme iron and manganese complexes are emerging as powerful and versatile catalysts in several oxidative transformations. Remarkable advantages associated with such catalysts are the ease of their synthesis and the related use of environmentally friendly compounds such as H2O2 as terminal oxidants. The most investigated non-heme iron- and manganese catalytic complexes are based on aminopyridine ligands, although a number of imine-based ligands have been recently considered. We have lately used a supramolecular approach in the field of aminopyridine-based iron and manganese complexes to catalyze the selective oxidation of particular methylenic positions of long, linear, primary amines. The binding event responsible of the recognition between the catalyst and the substrate allows for an unprecedented selectivity. Concerning the imine-based catalysts, we introduced an imine-based iron complex, easily prepared in situ from cheap and commercially available starting materials, which was demonstrated to be able to catalyze the oxidation of aliphatic and aromatic C−H bonds. We are currently investigating on the possible expansion of the synthetic scope of our supramolecular aminopyridine-based complex and on the mechanism of action of the imine-based iron complex.
Non-heme iron and manganese complexes are emerging as powerful and versatile catalysts in several oxidative transformations. Remarkable advantages associated with such catalysts are the ease of their synthesis and the related use of environmentally friendly compounds such as H2O2 as terminal oxidants. The most investigated non-heme iron- and manganese catalytic complexes are based on aminopyridine ligands, although a number of imine-based ligands have been recently considered. We have lately used a supramolecular approach in the field of aminopyridine-based iron and manganese complexes to catalyze the selective oxidation of particular methylenic positions of long, linear, primary amines. The binding event responsible of the recognition between the catalyst and the substrate allows for an unprecedented selectivity. Concerning the imine-based catalysts, we introduced an imine-based iron complex, easily prepared in situ from cheap and commercially available starting materials, which was demonstrated to be able to catalyze the oxidation of aliphatic and aromatic C−H bonds. We are currently investigating on the possible expansion of the synthetic scope of our supramolecular aminopyridine-based complex and on the mechanism of action of the imine-based iron complex.
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