Lorenzo Casimiro
@sorbonne-universite.fr
Institut Parisien de Chimie Moléculaire UMR8232 - Sorbonne Université
Sorbonne Université
Lorenzo Casimiro received his PhD in Chemistry in 2020 at the University of Bologna (Italy), under the supervision of Prof. Serena Silvi and Prof. Alberto Credi, in collaboration with the CLAN – Center for Light Activated Nanostructures. His PhD thesis, titled “Novel Photo- and Electro-responsive Supramolecular Systems and Molecular Machines” has received the European Photochemistry Association and the Italian Group of Photochemistry awards for the best PhD thesis in photochemistry. After spending 3 years as a post-doctoral fellow at the PPSM Laboratory in ENS Paris-Saclay (France), in the groups of Dr. Rémi Métivier and Dr. Clémence Allain, he currently holds a post-doctoral position in the E-POM team, at Sorbonne University, in Paris. His research activity focuses on photo-, electro-, and mechano-responsive inorganic or molecular, supra- and macro-molecular materials.
EDUCATION
Post-doctoral fellow at IPCM UMR8232 - Sorbonne Université, Paris, France
PhD in Chemistry at Alma Mater Studiorum - Università di Bologna, Bologna, Italy (2020)
MSc cum laude in Photochemistry and Molecular Materials at Alma Mater Studiorum - Università di Bologna, Bologna, Italy (2016)
BSc cum laude in Chemistry and Material Chemistry at Alma Mater Studiorum - Università di Bologna, Bologna, Italy (2014)
RESEARCH, TEACHING, or OTHER INTERESTS
Chemistry, Spectroscopy, Physical and Theoretical Chemistry, Inorganic Chemistry
Scopus Publications
Scholar Citations
Scholar h-index
Scholar i10-index
Scopus Publications
Lorenzo Casimiro, Rémi Métivier, Bruno Le Pioufle, Sakina Bensalem, and Clémence Allain
Wiley
AbstractPolydiacetylenes are deeply investigated for their mechanofluorochromic behavior: the blue, non‐emitting solid phase, obtained by photopolymerization of the diacetylene precursor, is converted to the red, emitting one by a mechanical stimulus. Inspired by the great potentiality of these compounds to act as microscale force probes, the mechanofluorochromism is implemented in microalgae biotechnology. Indeed, mechanical solicitations in a microfluidic chip can weaken the cellular envelope and facilitate the extraction of high‐added value compounds produced by the microalgae. Herewith, a polydiacetylene‐based mechanofluorochromic sensor is reported to be able to detect the stress applied to microalgae in microchannels. A triethoxysilane diacetylene precursor is designed that photopolymerizes in a purple, low‐emissive phase, and is converted to the red, high‐emissive phase upon mechanical stress. Hereafter, a protocol is set up to chemically graft in the microfluidic channels a polydiacetylene layer, and eventually proves that upon compression of Chlamydomonas reinhardtii microalgae in restricted areas, the friction stress is revealed by the mechanofluorochromic response of the polydiacetylene, leading to a marked fluorescence enhancement up to 83%. This prototype of microscale force probes lays the ground for microscale stress detection in microfluidics environments, which can be applied not only to microalgae but also to any mechano‐responsive cellular sample.
Lorenzo Casimiro, Leonardo Andreoni, Jessica Groppi, Alberto Credi, Rémi Métivier, and Serena Silvi
Springer Science and Business Media LLC
AbstractChemical actinometers are a useful tool in photochemistry, which allows to measure the photon flux of a light source to carry out quantitative analysis on photoreactions. The most commonly employed actinometers so far show minor drawbacks, such as difficult data treatment, parasite reactions, low stability or impossible reset. We propose herewith the use of 4,4′-dimethylazobenzene as a chemical actinometer. This compound undergoes a clean and efficient E/Z isomerization, approaching total conversion upon irradiation at 365 nm. Thanks to its properties, it can be used to determine the photon flux in the UV–visible region, with simple experimental methods and data treatment, and with the possibility to be reused after photochemical or thermal reset. Graphical abstract
Yang Zhou, Stéphane Maisonneuve, Lorenzo Casimiro, Pascal Retailleau, Juan Xie, François Maurel, and Rémi Métivier
Royal Society of Chemistry (RSC)
The effect of the four isomeric forms of DCM on its emission and photoreactivity is highlighted, based on a suitable combination of experimental data (structures and spectroscopy) and theoretical computations (DFT and spin–flip TDDFT).
Massimo Baroncini, Martina Canton, Lorenzo Casimiro, Alberto Credi, and Serena Silvi
Springer International Publishing
Nawel Goual, Lorenzo Casimiro, Vincent Delattre, Pascal Retailleau, Stéphane Maisonneuve, Nicolas Bogliotti, Rémi Métivier, Juan Xie, Angela Marinetti, and Arnaud Voituriez
Royal Society of Chemistry (RSC)
Dibenzotriazonines, a new class of nine-membered cyclic azobenzenes, have been developed and have demonstrated good thermal stability for both E- and Z-isomers.
Stefano Corra, Lorenzo Casimiro, Massimo Baroncini, Jessica Groppi, Marcello La Rosa, Marina Tranfić Bakić, Serena Silvi, and Alberto Credi
Wiley
AbstractInvited for the cover of this issue is Alberto Credi and co‐workers at the University of Bologna and National Research Council, Bologna, Italy. The image represents the photostationary non‐equilibrium operation of supramolecular pumps as a hydraulic circuit in which water flows between reservoirs. Read the full text of the article at 10.1002/chem.202101163.
Stefano Corra, Lorenzo Casimiro, Massimo Baroncini, Jessica Groppi, Marcello La Rosa, Marina Tranfić Bakić, Serena Silvi, and Alberto Credi
Wiley
AbstractThe development of artificial nanoscale motors that can use energy from a source to perform tasks requires systems capable of performing directionally controlled molecular movements and operating away from chemical equilibrium. Here, the design, synthesis and properties of pseudorotaxanes are described, in which a photon input triggers the unidirectional motion of a macrocyclic ring with respect to a non‐symmetric molecular axle. The photoinduced energy ratcheting at the basis of the pumping mechanism is validated by measuring the relevant thermodynamic and kinetic parameters. Owing to the photochemical behavior of the azobenzene moiety embedded in the axle, the pump can repeat its operation cycle autonomously under continuous illumination. NMR spectroscopy was used to observe the dissipative non‐equilibrium state generated in situ by light irradiation. We also show that fine changes in the axle structure lead to an improvement in the performance of the motor. Such results highlight the modularity and versatility of this minimalist pump design, which provides facile access to dynamic systems that operate under photoinduced non‐equilibrium regimes.
Martina Canton, Jessica Groppi, Lorenzo Casimiro, Stefano Corra, Massimo Baroncini, Serena Silvi, and Alberto Credi
American Chemical Society (ACS)
We describe the modular design of a pseudorotaxane-based supramolecular pump and its photochemically driven autonomous nonequilibrium operation in a dissipative regime. These properties derive from careful engineering of the energy maxima and minima along the threading coordinate and their light-triggered modulation. Unlike its precursor, this second-generation system is amenable to functionalization for integration into more complex devices.
Clément Cazorla, Lorenzo Casimiro, Tanzeel Arif, Claire Deo, Nawel Goual, Pascal Retailleau, Rémi Métivier, Juan Xie, Arnaud Voituriez, Angela Marinetti,et al.
Royal Society of Chemistry (RSC)
The synthesis, structural analysis and photochemical studies of azobenzene-diphosphine ligands and gold(i) complexes are reported.
Luka Ðorđević, Lorenzo Casimiro, Nicola Demitri, Massimo Baroncini, Serena Silvi, Francesca Arcudi, Alberto Credi, and Maurizio Prato
Wiley
AbstractMulti‐functionalization and isomer‐purity of fullerenes are crucial tasks for the development of their chemistry in various fields. In both current main approaches—tether‐directed covalent functionalization and supramolecular masks—the control of regioselectivity requires multi‐step synthetic procedures to prepare the desired tether or mask. Herein, we describe light‐responsive tethers, containing an azobenzene photoswitch and two malonate groups, in the double cyclopropanation of [60]fullerene. The formation of the bis‐adducts and their spectroscopic and photochemical properties, as well as the effect of azobenzene photoswitching on the regiochemistry of the bis‐addition, have been studied. The behavior of the tethers depends on the geometry of the connection between the photoactive core and the malonate moieties. One tether lead to a strikingly different adduct distribution for the E and Z isomers, indicating that the covalent bis‐functionalization of C60 can be controlled by light.
Lorenzo Casimiro, Stéphane Maisonneuve, Pascal Retailleau, Serena Silvi, Juan Xie, and Rémi Métivier
Wiley
AbstractAlthough 4‐dicyanomethylene‐2‐methyl‐6‐(p‐dimethylamino‐styryl)‐4H‐pyran (DCM) has been known for many decades as a bright and photostable fluorophore, used for a wide variety of applications in chemistry, biology and physics, only little attention has been paid so far to the presence of multiple isomers and conformers, namely s‐trans‐(E), s‐cis‐(E), s‐trans‐(Z), and s‐cis‐(Z). In particular, light‐induced E–Z isomerization plays a great role on the overall photophysical properties of DCM. Herein, we give a full description of a photoswitchable DCM derivative by a combination of structural, theoretical and spectroscopic methods. The main s‐trans‐(E) isomer is responsible for most of the fluorescence features, whereas the s‐cis‐(E) conformer only contributes marginally. The non‐emitting Z isomers are generated in large conversion yields upon illumination with visible light (e.g., 485 or 514 nm) and converted back to the E forms by UV irradiation (e.g., 365 nm). Such photoswitching is efficient and reversible, with high fatigue resistance. The E→Z and Z→E photoisomerization quantum yields were determined in different solvents and at different irradiation wavelengths. Interestingly, the fluorescence and photoisomerization properties are strongly influenced by the solvent polarity: the fluorescence is predominant at higher polarity, whereas photoisomerization becomes more efficient at lower polarity. Intermediate medium (THF) represents an optimized situation with a good balance between these two features.
Jessica Groppi, Lorenzo Casimiro, Martina Canton, Stefano Corra, Mina Jafari‐Nasab, Gloria Tabacchi, Luigi Cavallo, Massimo Baroncini, Serena Silvi, Ettore Fois,et al.
Wiley
AbstractThe general principles guiding the design of molecular machines based on interlocked structures are well known. Nonetheless, the identification of suitable molecular components for a precise tuning of the energetic parameters that determine the mechanical link is still challenging. Indeed, what are the reasons of the “all‐or‐nothing” effect, which turns a molecular “speed‐bump” into a stopper in pseudorotaxane‐based architectures? Here we investigate the threading and dethreading processes for a representative class of molecular components, based on symmetric dibenzylammonium axles and dibenzo[24]crown‐8 ether, with a joint experimental–computational strategy. From the analysis of quantitative data and an atomistic insight, we derive simple rules correlating the kinetic behaviour with the substitution pattern, and provide rational guidelines for the design of modules to be integrated in molecular switches and motors with sophisticated dynamic features.
Guido Orlandini, Lorenzo Casimiro, Margherita Bazzoni, Beatrice Cogliati, Alberto Credi, Marco Lucarini, Serena Silvi, Arturo Arduini, and Andrea Secchi
Royal Society of Chemistry (RSC)
A self-complexing lasso-like molecule has been synthesised as the first example of a calix[6]arene-based [1]pseudorotaxane. This artificial molecular lasso can be switched between self-threaded and dethreaded structures by redox stimulation.
Margherita Bazzoni, Valeria Zanichelli, Lorenzo Casimiro, Chiara Massera, Alberto Credi, Andrea Secchi, Serena Silvi, and Arturo Arduini
Wiley
Understanding the role played by the nature, number, and arrangement of binding sites anchored to a macrocycle remains a topic of current interest for the synthesis of new interwoven species. We report the synthesis and detailed structural characterization of a new calix[6]arene derivative decorated with two phenylureido groups anchored at the diametrical position of the calix upper rim that adopts a 1,2,3‐alternate conformation in solution and in the solid state. Preliminary data on the ability of this host to form redox‐active pseudorotaxanes and rotaxanes are reported.
Giorgio Baggi, Lorenzo Casimiro, Massimo Baroncini, Serena Silvi, Alberto Credi, and Stephen J. Loeb
Royal Society of Chemistry (RSC)
Photochromic axles bearing a bis(thienyl)ethene moiety exhibit threading-gated photochromism, where formation of a [2]pseudorotaxane with crown ether rings significantly enhances the photochromic properties of the axles.
Massimo Baroncini, Martina Canton, Lorenzo Casimiro, Stefano Corra, Jessica Groppi, Marcello La Rosa, Serena Silvi, and Alberto Credi
Wiley
Molecular and supramolecular‐based systems and materials that can perform predetermined functions in response to light stimulation have been extensively studied in the past three decades. Their investigation continues to be a highly stimulating topic of chemical research, not only because of the inherent scientific value related to a bottom‐up approach to functional nanostructures, but also for the prospective applications in diverse fields of technology and medicine. Light is an important tool in this context, as it can be conveniently used both for supplying energy to the system and for probing its states and transformations. In this microreview we recall some basic aspects of light‐induced processes in (supra)molecular assemblies, and discuss their exploitation to implement novel functionalities with nanostructured devices, machines and materials. To this aim we illustrate a few examples from our own recent work, which are meant to illustrate the trends of current research in the field.
Massimo Baroncini, Lorenzo Casimiro, Christiaan de Vet, Jessica Groppi, Serena Silvi, and Alberto Credi
Wiley
AbstractMovement is one of the central attributes of life, and a key feature in many technological processes. While artificial motion is typically provided by macroscopic engines powered by internal combustion or electrical energy, movement in living organisms is produced by machines and motors of molecular size that typically exploit the energy of chemical fuels at ambient temperature to generate forces and ultimately execute functions. The progress in several areas of chemistry, together with an improved understanding of biomolecular machines, has led to the development of a large variety of wholly synthetic molecular machines. These systems have the potential to bring about radical innovations in several areas of technology and medicine. In this Minireview, we discuss, with the help of a few examples, the multidisciplinary aspects of research on artificial molecular machines and highlight its translational character.
Lorenzo Casimiro, Jessica Groppi, Massimo Baroncini, Marcello La Rosa, Alberto Credi, and Serena Silvi
Springer Science and Business Media LLC
Among the plethora of photochromes reported so far, azobenzene has been proven to be the most suitable photoswitch for molecular systems and materials, due to its highly efficient and clean E-Z photoisomerization. Here we report two ammonium-based molecular axles bearing one or two p -cyanoazobenzene units at the extremities, able to form pseudorotaxanes with a crown ether macrocycle. The photochemistry of these compounds was studied in the isolated forms and in the pseudorotaxanes, showing that the functionalization speeds up the threading process without affecting the photochemical properties of the system. These results suggest that the investigated pseudorotaxanes can form the basis of new prototypes of artificial molecular-level pumps.