• PhD in Molecular Sciences (curriculum Chemical Sciences), Cum laude. University of Padova (2019-2023, Italy).
• Master Degree in Chemistry, (mark: 110/110 Cum laude). University of Padova (2016-2019, Italy).
• Bachelor Degree in Chemistry, (mark: 110/110). University of Padova (2013-2016, Italy)
RESEARCH, TEACHING, or OTHER INTERESTS
Organic Chemistry, Chemistry
12
Scopus Publications
Scopus Publications
Circular Dichroism Reveals Positive Cooperativity through Compensatory Motion in Stepwise Cage Metalation Melvin Raulin, Chiara Slaviero, Federico Begato, Giulia Licini, Cristiano Zonta Inorganic Chemistry, 2026 High Resolution Image Download MS PowerPoint Slide Biological allosteric systems achieve functional control through long-range communication between distant binding sites. Here, we report that a symmetric chiral cage bearing two equivalent tris(2-pyridylmethyl)amine ( TPMA ) binding sites exhibits structural communication reminiscent of allosteric behavior during stepwise Zn(II) coordination. NMR titrations reveal sequential metalation kinetics in which the second coordination step becomes comparatively slower in mixed solvents, consistent with electrostatic effects and structural preorganization. Circular dichroism (CD) spectroscopy tracks the progressive structural evolution of the cage, with five isodichroic points confirming clean interconversion between discrete species. TD-DFT calculations reproduce the experimental chiroptical evolution, and correlate the observed spectral changes with systematic geometric reorganization of the framework over distances exceeding 10 Å. This work illustrates the potential of CD spectroscopy as a diagnostic tool for probing allosteric-like mechanisms in synthetic supramolecular systems, with implications for heterometallic catalysis, responsive materials, and allosteric synthetic receptors.
Confined metal centres in a symmetric cage: mono- and heterodinuclear complexes for photocatalytic hydrogen evolution Melvin Raulin, Federico Droghetti, Davide Zeppilli, Federico Begato, Pradip Kumar Mondal, Marzio Rancan, Giulia Licini, Laura Orian, Mirco Natali, Cristiano Zonta Inorganic Chemistry Frontiers, 2026 Selective mono-, homo- and heterodinuclear metalation is achieved within a chiral TPMA cage, offering a unified platform to disentangle confinement, nuclearity and second-sphere proton-relay effects in photocatalytic hydrogen evolution.
Substituent Flexibility Modulates Aggregation-Induced Emission in Tetraphenylbenzene Vincent Monnier, Federico Begato, Aurelio Mateo-Alonso Organic Letters, 2025 Among the existing aggregation-induced emission luminogen archetypes, tetraphenylbenzene is one of the simplest and less studied for its aggregation-induced emission properties. In this study, we give insight into the structure–AIE relationship, focusing on the functionalization of the two free para positions of the benzene core of tetraphenylbenzene. Our study reveals that the flexibility and rigidity of the para substituents noticeably impact the aggregation-induced emission expression, allowing the inducement of either aggregation-induced emission enhancement or pure aggregation-induced emission.
Strong Enhancement in Cobalt(II)-TPMA Aqueous Hydrogen Photosynthesis through Intramolecular Proton Relay Federico Droghetti, Federico Begato, Melvin Raulin, Gioia Musiu, Giulia Licini, Mirco Natali, Cristiano Zonta Angewandte Chemie International Edition, 2024 Photosynthetic hydrogen generation by cobalt(II) tris(2‐pyridylmethyl)amine (TPMA) complexes is mainly limited by protonation kinetics and decomposition routes involving demetallation. In the present work we have explored the effects of both proton shuttles and improved rigidity on the catalytic ability of cobalt(II) TPMA complexes. Remarkably, we demonstrate that, while a small enhancement in the catalytic performance is attained in a rigid cage structure, the introduction of ammonium groups as proton transfer relays in close proximity to the cobalt center allows to reach a 4‐fold increase in the quantum efficiency of H2 formation, and a surprising 22‐fold gain in the maximum turnover number, at low catalyst concentration. The beneficial role of the ammonium relays in promoting faster intramolecular proton transfer to the reduced cobalt center is documented by transient absorption spectroscopy, showcasing the great relevance of tuning the catalyst periphery to achieve efficient catalysis of solar fuel formation.
Exploiting Chirality in Confined Nanospaces Federico Begato, Giulia Licini, Cristiano Zonta Angewandte Chemie International Edition, 2023 Spatial organization using confinement has been of great interest since the early ages of supramolecular chemistry. Application such as sensing, catalysis and delivery are continuously emerging. This minireview highlights the evolution of chiral supramolecular cages (CSC) applications in the fields of catalysis, sensing and chiroptical properties. More in detail, beside the description of the strategies adopted for the preparation of chiral supramolecular cages, either of purely organic supramolecular architectures or prepared using metal‐ligand coordination bonds, recent findings on their applications, with particular attention to stereodynamic systems, are presented to highlight the recent scientific interests and the future opportunities.
Combining Imine Condensation Chemistry with [3,3] Diaza-Cope Rearrangement for One-Step Formation of Hydrolytically Stable Chiral Architectures Federico Begato, Roberto Penasa, Klaus Wurst, Giulia Licini, Cristiano Zonta Angewandte Chemie International Edition, 2023 Dynamic covalent chemistry (DCC) has, in recent years, provided valuable tools to synthesize molecular architectures of increasing complexity. We have also taken advantage of imine DCC chemistry to prepare TPMA‐based supramolecular cages for molecular recognition applications. However, the versatility of this approach has as a major drawback the intrinsic hydrolytic lability of imines, which hampers some applications. We present herein a synthetic strategy that combines the advantages of a thermodynamic‐driven formation of a supramolecular structure using imine chemistry, together with the possibility to synthetize chiral hydrolytically stable structures through a [3,3]‐sigmatropic rearrangement. A preliminary mechanistic analysis of this one‐pot synthesis and the scope of the reaction are also discussed.
Programmed guest confinement via hierarchical cage to cage transformations Federico Begato, Giulia Licini, Cristiano Zonta Chemical Science, 2023 A novel methodology based on the use of phenanthrenequinone is applied to selectively change the subcomponent of TPMA-based cages, thus controlling inclusion ratio of competing guests differing in size or chirality.
Fluorescence detected circular dichroism (FDCD) of a stereodynamic probe Roberto Penasa, Federico Begato, Giulia Licini, Klaus Wurst, Sergio Abbate, Giovanna Longhi, Cristiano Zonta Chemical Communications, 2023 Fluorescence detected circular dichroism (FDCD) has been used to determine e.e. of carboxylic acids at sensor concentrations down to 0.1 μM also in the presence of chiroptical active contaminants.
Chiroptical Enhancement of Chiral Dicarboxylic Acids from Confinement in a Stereodynamic Supramolecular Cage Federico Begato, Roberto Penasa, Giulia Licini, Cristiano Zonta ACS Sensors, 2022 The fundamental implications that chirality has in science and technology require continuous efforts for the development of fast, economic, and reliable quantitative methods for enantiopurity assessment. Among the different analytical approaches, chiroptical techniques in combination with supramolecular methodologies have shown promising results in terms of both costs and time analysis. In this article, a tris(2-pyridylmethyl)amines (TPMA)-based supramolecular cage is able to amplify the circular dichroism (CD) signal of a series of chiral dicarboxylic acids also in the presence of a complex mixture. This feature has been used to quantify tartaric acid in wines and to discriminate different matrixes using principal component analysis (PCA) of the raw CD data.
