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
Rotaxane-catalyzed aerobic oxidation of primary alcohols Ilario Baù, Cecilia Poderi, Francesca Sardu, Alessia Giancola, Anna Turchetti, et al. Communications Chemistry, 2024 Nitroxide radicals are widely utilized as catalysts for the oxidation of primary alcohols. Here, the aerobic catalytic oxidation cycle of nitroxide radicals has been implemented within a mechanically interlocked rotaxane architecture consisting of a paramagnetic crown ether, which is confined by a molecular axle containing a dialkylammonium station and a 1,2,3-triazole unit. The rotaxane is engineered to exploit the oxidation of a primary alcohol: the primary catalyst is the wheel, a nitroxide radical capable of altering its oxidation state during the catalytic cycle, while the co-oxidant is the Cerium(IV)/O2 couple. The synthesis of the proposed rotaxane, along with its characterization using EPR, HRMS, voltammetry and NMR data, is reported in the paper. The aerobic catalytic oxidation cycle was further investigated using EPR, NMR and GC-MS analyses. This study can aid in the design of autonomously driven molecular machines that exploit the aerobic catalytic oxidation of nitroxide radicals.
Revealing the Friction Stress of Microalgae in Microfluidic Devices through Mechanofluorochromism Lorenzo Casimiro, Rémi Métivier, Bruno Le Pioufle, Sakina Bensalem, Clémence Allain Advanced Materials Interfaces, 2023 Polydiacetylenes 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.
4,4′-Dimethylazobenzene as a chemical actinometer Lorenzo Casimiro, Leonardo Andreoni, Jessica Groppi, Alberto Credi, Rémi Métivier, et al. Photochemical and Photobiological Sciences, 2022 Chemical 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
Triazonine-based bistable photoswitches: synthesis, characterization and photochromic properties Nawel Goual, Lorenzo Casimiro, Vincent Delattre, Pascal Retailleau, Stéphane Maisonneuve, et al. Chemical Communications, 2021 Dibenzotriazonines, a new class of nine-membered cyclic azobenzenes, have been developed and have demonstrated good thermal stability for both E- and Z-isomers.
Artificial Supramolecular Pumps Powered by Light Stefano Corra, Lorenzo Casimiro, Massimo Baroncini, Jessica Groppi, Marcello La Rosa, et al. Chemistry Weinheim an Der Bergstrasse Germany, 2021 Invited 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.
Artificial Supramolecular Pumps Powered by Light Stefano Corra, Lorenzo Casimiro, Massimo Baroncini, Jessica Groppi, Marcello La Rosa, et al. Chemistry A European Journal, 2021 The 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.
Second-Generation Light-Fueled Supramolecular Pump Martina Canton, Jessica Groppi, Lorenzo Casimiro, Stefano Corra, Massimo Baroncini, et al. Journal of the American Chemical Society, 2021 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.
Precision Molecular Threading/Dethreading Jessica Groppi, Lorenzo Casimiro, Martina Canton, Stefano Corra, Mina Jafari‐Nasab, et al. Angewandte Chemie International Edition, 2020
Multifunctional Supramolecular Gels with Strong Mechanical Properties Formed by Self-Assembly of Polyoxometalate-Based Coordination Polymers L Casimiro, F Volatron, G Boivin, B Abécassis, S Alves, D Brouri, ... JACS Au 4 (12), 4948-4956 , 2024 2024 Citations: 11
Rotaxane-catalyzed aerobic oxidation of primary alcohols I Baù, C Poderi, F Sardu, A Giancola, A Turchetti, P Franchi, L Casimiro, ... Communications Chemistry 7 (1), 278 , 2024 2024 Citations: 3
The butterfly effect of photochromes L Casimiro 2023
Revealing the friction stress of microalgae in microfluidic devices through mechanofluorochromism L Casimiro, R Métivier, B Le Pioufle, S Bensalem, C Allain Advanced Materials Interfaces 10 (31), 2300312 , 2023 2023 Citations: 10
4, 4′-Dimethylazobenzene as a chemical actinometer L Casimiro, L Andreoni, J Groppi, A Credi, R Métivier, S Silvi Photochemical & Photobiological Sciences 21 (5), 825-833 , 2022 2022 Citations: 18
Mechanically Interlocked Systems: Photoactive Rotaxanes and Catenanes SS Massimo Baroncini, Martina Canton, Lorenzo Casimiro, Alberto Credi Springer Handbook of Inorganic Photochemistry, 585–602 , 2022 2022
Photoisomerization of a 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4 H-pyran analog dye: a combined photophysical and theoretical investigation Y Zhou, S Maisonneuve, L Casimiro, P Retailleau, J Xie, F Maurel, ... Physical Chemistry Chemical Physics 24 (10), 6282-6289 , 2022 2022 Citations: 4
Front Cover: Artificial Supramolecular Pumps Powered by Light (Chem. Eur. J. 43/2021) S Corra, L Casimiro, M Baroncini, J Groppi, M La Rosa, M Tranfić Bakić, ... Chemistry–A European Journal 27 (43), 11015-11015 , 2021 2021
Artificial supramolecular pumps powered by light S Corra, L Casimiro, M Baroncini, J Groppi, M La Rosa, M Tranfić Bakić, ... Chemistry–A European Journal 27 (43), 11076-11083 , 2021 2021 Citations: 37
Second-generation light-fueled supramolecular pump M Canton, J Groppi, L Casimiro, S Corra, M Baroncini, S Silvi, A Credi Journal of the American Chemical Society 143 (29), 10890-10894 , 2021 2021 Citations: 54
Light‐Controlled Regioselective Synthesis of Fullerene Bis‐Adducts L Ðorđević, L Casimiro, N Demitri, M Baroncini, S Silvi, F Arcudi, A Credi, ... Angewandte Chemie International Edition 60 (1), 313-320 , 2021 2021 Citations: 37
Triazonine-based bistable photoswitches: synthesis, characterization and photochromic properties N Goual, L Casimiro, V Delattre, P Retailleau, S Maisonneuve, N Bogliotti, ... Chemical Communications 57 (78), 10079-10082 , 2021 2021 Citations: 7
Synthesis and properties of photoswitchable diphosphines and gold (I) complexes derived from azobenzenes C Cazorla, L Casimiro, T Arif, C Deo, N Goual, P Retailleau, R Métivier, ... Dalton Transactions 50 (21), 7284-7292 , 2021 2021 Citations: 11
Front Cover: Photophysical Properties of 4‐Dicyanomethylene‐2‐methyl‐6‐( p ‐dimethylamino‐styryl)‐4 H ‐pyran Revisited: Fluorescence versus … L Casimiro, S Maisonneuve, P Retailleau, S Silvi, J Xie, R Métivier Chemistry–A European Journal 26 (63), 14252-14252 , 2020 2020
Photophysical Properties of 4‐Dicyanomethylene‐2‐methyl‐6‐( p ‐dimethylamino‐styryl)‐4 H ‐pyran Revisited: Fluorescence versus Photoisomerization L Casimiro, S Maisonneuve, P Retailleau, S Silvi, J Xie, R Métivier Chemistry–A European Journal 26 (63), 14341-14350 , 2020 2020 Citations: 18
Precision molecular threading/dethreading J Groppi, L Casimiro, M Canton, S Corra, M Jafari‐Nasab, G Tabacchi, ... Angewandte Chemie 132 (35), 14935-14944 , 2020 2020 Citations: 55
Novel photo-and electro-responsive supramolecular systems and molecular machines L Casimiro alma , 2020 2020
Novel Photo- and Electro-responsive Supramolecular Systems and Molecular Machines L Casimiro EPA Newsletter 97, 59-63 , 2020 2020
ChemistryOpen 2018, 7, 169–179; e) M. Baroncini, S. Silvi, A. Credi M Baroncini, L Casimiro, C de Vet, J Groppi Chem. Rev 120, 200-268 , 2020 2020 Citations: 7
Tunable Photochromic Building Blocks for Molecular Machines and Supramolecular Systems L Casimiro EPA Newsletter 99, 38-41 , 2020 2020
MOST CITED SCHOLAR PUBLICATIONS
Making and operating molecular machines: a multidisciplinary challenge M Baroncini, L Casimiro, C De Vet, J Groppi, S Silvi, A Credi ChemistryOpen 7 (2), 169-179 , 2018 2018 Citations: 106
Precision molecular threading/dethreading J Groppi, L Casimiro, M Canton, S Corra, M Jafari‐Nasab, G Tabacchi, ... Angewandte Chemie 132 (35), 14935-14944 , 2020 2020 Citations: 55
Second-generation light-fueled supramolecular pump M Canton, J Groppi, L Casimiro, S Corra, M Baroncini, S Silvi, A Credi Journal of the American Chemical Society 143 (29), 10890-10894 , 2021 2021 Citations: 54
Artificial supramolecular pumps powered by light S Corra, L Casimiro, M Baroncini, J Groppi, M La Rosa, M Tranfić Bakić, ... Chemistry–A European Journal 27 (43), 11076-11083 , 2021 2021 Citations: 37
Light‐Controlled Regioselective Synthesis of Fullerene Bis‐Adducts L Ðorđević, L Casimiro, N Demitri, M Baroncini, S Silvi, F Arcudi, A Credi, ... Angewandte Chemie International Edition 60 (1), 313-320 , 2021 2021 Citations: 37
Photoactive Molecular‐Based Devices, Machines and Materials: Recent Advances M Baroncini, M Canton, L Casimiro, S Corra, J Groppi, M La Rosa, S Silvi, ... European Journal of Inorganic Chemistry 2018 (42), 4589-4603 , 2018 2018 Citations: 33
Threading-gated photochromism in [2] pseudorotaxanes G Baggi, L Casimiro, M Baroncini, S Silvi, A Credi, SJ Loeb Chemical Science 10 (19), 5104-5113 , 2019 2019 Citations: 26
4, 4′-Dimethylazobenzene as a chemical actinometer L Casimiro, L Andreoni, J Groppi, A Credi, R Métivier, S Silvi Photochemical & Photobiological Sciences 21 (5), 825-833 , 2022 2022 Citations: 18
Photophysical Properties of 4‐Dicyanomethylene‐2‐methyl‐6‐( p ‐dimethylamino‐styryl)‐4 H ‐pyran Revisited: Fluorescence versus Photoisomerization L Casimiro, S Maisonneuve, P Retailleau, S Silvi, J Xie, R Métivier Chemistry–A European Journal 26 (63), 14341-14350 , 2020 2020 Citations: 18
Photochemical investigation of cyanoazobenzene derivatives as components of artificial supramolecular pumps L Casimiro, J Groppi, M Baroncini, M La Rosa, A Credi, S Silvi Photochemical & Photobiological Sciences 17 (6), 734-740 , 2018 2018 Citations: 17
Synthesis and properties of a redox-switchable calix [6] arene-based molecular lasso G Orlandini, L Casimiro, M Bazzoni, B Cogliati, A Credi, M Lucarini, S Silvi, ... Organic Chemistry Frontiers 7 (4), 648-659 , 2020 2020 Citations: 14
New Geometries for Calix [6] arene‐Based Rotaxanes M Bazzoni, V Zanichelli, L Casimiro, C Massera, A Credi, A Secchi, S Silvi, ... European Journal of Organic Chemistry 2019 (21), 3513-3524 , 2019 2019 Citations: 12
Multifunctional Supramolecular Gels with Strong Mechanical Properties Formed by Self-Assembly of Polyoxometalate-Based Coordination Polymers L Casimiro, F Volatron, G Boivin, B Abécassis, S Alves, D Brouri, ... JACS Au 4 (12), 4948-4956 , 2024 2024 Citations: 11
Synthesis and properties of photoswitchable diphosphines and gold (I) complexes derived from azobenzenes C Cazorla, L Casimiro, T Arif, C Deo, N Goual, P Retailleau, R Métivier, ... Dalton Transactions 50 (21), 7284-7292 , 2021 2021 Citations: 11
Revealing the friction stress of microalgae in microfluidic devices through mechanofluorochromism L Casimiro, R Métivier, B Le Pioufle, S Bensalem, C Allain Advanced Materials Interfaces 10 (31), 2300312 , 2023 2023 Citations: 10
Triazonine-based bistable photoswitches: synthesis, characterization and photochromic properties N Goual, L Casimiro, V Delattre, P Retailleau, S Maisonneuve, N Bogliotti, ... Chemical Communications 57 (78), 10079-10082 , 2021 2021 Citations: 7
ChemistryOpen 2018, 7, 169–179; e) M. Baroncini, S. Silvi, A. Credi M Baroncini, L Casimiro, C de Vet, J Groppi Chem. Rev 120, 200-268 , 2020 2020 Citations: 7
Photoisomerization of a 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4 H-pyran analog dye: a combined photophysical and theoretical investigation Y Zhou, S Maisonneuve, L Casimiro, P Retailleau, J Xie, F Maurel, ... Physical Chemistry Chemical Physics 24 (10), 6282-6289 , 2022 2022 Citations: 4
Rotaxane-catalyzed aerobic oxidation of primary alcohols I Baù, C Poderi, F Sardu, A Giancola, A Turchetti, P Franchi, L Casimiro, ... Communications Chemistry 7 (1), 278 , 2024 2024 Citations: 3
The butterfly effect of photochromes L Casimiro 2023