Handedness in Inherently Chiral Heterocyclic Systems: Synthesis, Supramolecular Assembly, andTheir Chiroptical and Electrochemical Properties as Platforms for Advanced Functional Materials— HANDS
ProjectHANDS project will develop inherently chiral heterocyclic molecular and supramolecular systems in which redox-active, photophysical and spin-dependent functions are embedded within well-defined helicene-based chiral architectures. The project will move from molecular design tohierarchical organization, exploring how handedness can be encoded at the molecular level,amplified through supramolecular aggregation, and probed or modulated by redox andphotochemical stimuli.
The synthetic core will build on the complementary expertise of UNIFI and UNIBO. UNIFI willdevelop azaheterohelicenes and dithia-bridged hetero[4]helicenes, including redox-activescaffolds capable of generating stable radical cations. UNIBO will introduce photocatalytic homologative strategies, azaborine-based helicenoids and boron-nitrogen chiral architectures.These platforms will be elaborated into dimers, donor–acceptor dyads, glyco- and peptido-conjugates, macromolecular derivatives, and helicene–porphyrin or helicene–boraporphyrinhybrids. This diversity will clarify how heteroatom composition, bridge topology, oxidation stateand supramolecular environment influence charge delocalization, spin distribution, chiropticalresponse and aggregation behaviour.
Advanced characterization will connect molecular structure, chirality and function. UNIBS will leadchiroptical, photophysical and magnetic spectroscopic studies, combining vibrational andelectronic circular dichroism with magnetic circular dichroism, (magnetic) circularly polarizedluminescence and even magnetochiral dichroism to monitor spectroscopic response evolutionupon oxidation, aggregation in solution, and film formation. UNISI will investigate theelectrochemical and spectro-electrochemical behaviour of the redox-active architectures, definingthe stability, reversibility and electronic communication of neutral, charged and open-shell states. UNIME will study supramolecular organization and aggregation kinetics across three levels ofcomplexity: individual helicene-based systems, dimeric architectures, and coupled helicene–porphyrin or helicene–boraporphyrin hybrids. Co-assembly with charged porphyrins or porphyrinJ-aggregates, will provide models for handedness transfer and cooperative chiral amplification.
By integrating synthetic innovation, electrochemistry, advanced chiroptical and magneticspectroscopy, and supramolecular chemistry, HANDS will establish structure–propertyrelationships across molecular, macromolecular and supramolecular levels. The project willdeliver new families of redox-switchable and aggregation-controlled chiral platforms and providedesign principles for circularly polarized emitters, spin-selective molecular layers, magneto-chiroptical systems and advanced functional materials. HANDS will thus advance fundamentalunderstanding of how molecular handedness can be generated, transferred, amplified andexploited across increasing levels of structural complexity.
The synthetic core will build on the complementary expertise of UNIFI and UNIBO. UNIFI willdevelop azaheterohelicenes and dithia-bridged hetero[4]helicenes, including redox-activescaffolds capable of generating stable radical cations. UNIBO will introduce photocatalytic homologative strategies, azaborine-based helicenoids and boron-nitrogen chiral architectures.These platforms will be elaborated into dimers, donor–acceptor dyads, glyco- and peptido-conjugates, macromolecular derivatives, and helicene–porphyrin or helicene–boraporphyrinhybrids. This diversity will clarify how heteroatom composition, bridge topology, oxidation stateand supramolecular environment influence charge delocalization, spin distribution, chiropticalresponse and aggregation behaviour.
Advanced characterization will connect molecular structure, chirality and function. UNIBS will leadchiroptical, photophysical and magnetic spectroscopic studies, combining vibrational andelectronic circular dichroism with magnetic circular dichroism, (magnetic) circularly polarizedluminescence and even magnetochiral dichroism to monitor spectroscopic response evolutionupon oxidation, aggregation in solution, and film formation. UNISI will investigate theelectrochemical and spectro-electrochemical behaviour of the redox-active architectures, definingthe stability, reversibility and electronic communication of neutral, charged and open-shell states. UNIME will study supramolecular organization and aggregation kinetics across three levels ofcomplexity: individual helicene-based systems, dimeric architectures, and coupled helicene–porphyrin or helicene–boraporphyrin hybrids. Co-assembly with charged porphyrins or porphyrinJ-aggregates, will provide models for handedness transfer and cooperative chiral amplification.
By integrating synthetic innovation, electrochemistry, advanced chiroptical and magneticspectroscopy, and supramolecular chemistry, HANDS will establish structure–propertyrelationships across molecular, macromolecular and supramolecular levels. The project willdeliver new families of redox-switchable and aggregation-controlled chiral platforms and providedesign principles for circularly polarized emitters, spin-selective molecular layers, magneto-chiroptical systems and advanced functional materials. HANDS will thus advance fundamentalunderstanding of how molecular handedness can be generated, transferred, amplified andexploited across increasing levels of structural complexity.