Article
Chemistry, Multidisciplinary
Wiebke Alex, Patrick Lorenz, Christian Henkel, Timothy Clark, Andreas Hirsch, Dirk M. Guldi
Summary: This study provides a detailed understanding of the full reaction coordinate of NBDs to QCs and reveals that the photoreversibility of NBDs is influenced by the charge-transfer character.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Christoph Dohmen, Heiko Ihmels, Thomas Paululat
Summary: A dinaphthoylmethyl-substituted bullvalene derivative was studied for its excimer fluorescence properties. The host-guest interactions with metal cations were analyzed using fluorescent spectroscopy to monitor externally induced structural changes. Coincidentally, three unknown lumibullvalene isomers were discovered during the synthesis, and their emission properties were evaluated as reference compounds for the fluxional bullvalenes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Mayumi Chida, Satoru Takahashi, Ryunosuke Konishi, Takeshi Matsumoto, Akinobu Nakada, Masanori Wakizaka, Wataru Kosaka, Hitoshi Miyasaka, Ho-Chol Chang
Summary: The study demonstrated the tunability of molecular valence tautomerism and macroscopic solid-liquid transitions by optimizing chain design, and proposed a new strategy for coupling bistable molecules with the macroscopic world.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Alessandro Marotta, Hao Fang, Callum E. Adams, Kailey Sun Marcus, Constantin G. Daniliuc, John J. Molloy
Summary: Operationally simple strategies using visible light and a simple Lewis base are disclosed for the facile activation of α-halo boronic esters, leading to the construction of versatile E-allylic boronic esters via intermolecular addition to styrenes. This activation method can be strategically merged with selective energy transfer catalysis for the complimentary stereodivergent synthesis of Z-allylic boronic esters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Noah Jeremias, Lisa-Marie Mohr, Thorsten Bach
Summary: 2-Aryl-1-sulfonyl-substituted cyclobutanes were synthesized via an intermolecular [2 + 2] photocycloaddition using various alpha,beta-unsaturated sulfones and olefins. Lewis acids were employed to catalyze this reaction, with chiral-at-metal Lewis acid achieving enantioselective outcomes up to 77% ee.
Article
Chemistry, Multidisciplinary
Thi Minh Thi Le, Thibaud Bregent, Philippe Jubault, Thomas Poisson
Summary: In this study, we revealed the contra-thermodynamic E -> Z isomerization of alkenyl silanes by in situ formation of a chromophoric species, using rac-BINAP as the catalyst. The reaction, carried out in DMSO or CH3CN under irradiation at 405 nm, achieved the interconversion of E-isomers into Z-congeners with good to excellent yields and outstanding Z/E selectivities in 18 examples. Finally, the mechanism of the E -> Z isomerization was investigated to gain insights into the reaction mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Thibaud Bregent, Jean-Philippe Bouillon, Thomas Poisson
Summary: The photocatalytic contra-thermodynamic E -> Z isomerization of vinyl boronates can be achieved using a binaphthol catalyst. The reaction proceeds through the transient formation of a suitable chromophore with a BINOL derivative as the catalyst, resulting in good-to-excellent Z/E ratio and excellent-to-quantitative yields. The mechanism involves the formation of a transient chromophore species.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Spectroscopy
M. Pagacz-Kostrzewa, W. Szaniawska, M. Wierzejewska
Summary: The molecular structure, near-infrared (NIR), and ultraviolet (UV) induced phototransformations of indazole-3-carboxylic acid were investigated in low temperature argon and nitrogen matrices using FTIR spectroscopy and B3LYP/6-311++G(2d,2p) calculations. Eleven stable structures were identified on the S0 potential energy surface, and the three most stable structures were confirmed experimentally in both matrices. NIR irradiation induced rotamerization within the carboxylic group, resulting in changes in the populations of trans 1HIC1 and cis 1HIC2 forms. UV irradiation at λ = 260 nm generated two new tautomers (2HIC2 and 2HIC3), indicating hydrogen atom transfer in the pyrazole ring. The obtained kinetic curves suggested differences in the phototransformation rates between different matrices.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Chemistry, Multidisciplinary
Fei Tong, Daichi Kitagawa, Ibraheem Bushnak, Rabih O. Al-Kaysi, Christopher J. Bardeen
Summary: This study demonstrates that (Z)-DVAM molecular crystalline microwires can exhibit continuous oscillatory motion when exposed to a combination of ultraviolet and visible light, mimicking the behavior of biological flagella. This is the first example of molecular crystals showing complex oscillatory behavior under continuous irradiation, with rotational frequency depending on light intensity and polarization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daniel Hugenbusch, Marc Lehr, Jan-Simon von Glasenapp, Anna J. McConnell, Rainer Herges
Summary: We report the photo-switching properties of two regioisomeric diazocine ligands. The self-assembly of these ligands with Co-II ions was studied, and reversible transformation between different ligand configurations and Co-II complexes was achieved through light-controlled switching.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Tobias Morack, Carina Onneken, Hiroshi Nakakohara, Christian Mueck-Lichtenfeld, Ryan Gilmour
Summary: Researchers have developed a platform for enantioselective prenylation using light, aiming to facilitate chiral drug discovery. Detailed mechanistic analysis has led to the development of an efficient method for preparing enantioselective variants. The chiral pool quasi-enantiomers quinine and quinidine play an important role as catalysts in this process.
Article
Chemistry, Multidisciplinary
Miguel Sanz-Novo, Mauro Mato, Iker Leon, Antonio M. Echavarren, Jose L. Alonso
Summary: This study reports the valence tautomerism phenomena in the barbaralone molecular system, with two distinct tautomers successfully isolated and characterized using high-resolution rotational spectroscopy. The experimental evidence of the rearrangement in barbaralones is provided, highlighting the application of rotational spectroscopy in analyzing shape-shifting mixtures. Furthermore, this observation opens up new possibilities for characterizing new fluxional systems in the gas phase and contributes to the general understanding of valence tautomerism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
A. A. Zolotukhin, M. P. Bubnov, R. V. Rumyantsev, G. K. Fukin, A. S. Bogomyakov, V. K. Cherkasov
Summary: Two new cobalt bis-o-semiquinonato complexes, (Pyz-Phen)Co(3,6-DBSQ)(2) (I) and (Bpyz)Co(3,6-DBSQ)(2) (II), were synthesized and their structures were determined by X-ray diffraction analysis. The complexes exhibit a trigonal-prismatic geometry of the inner coordination sphere. The distribution of C-O and Co-O bond lengths suggests that the complexes consist of cobalt(II) ion coordinated with two semiquinone radical anions. Magnetic measurements reveal that (Pyz-Phen)Co(3,6-DBSQ)(2) is a low-spin divalent cobalt derivative, while (Bpyz)Co(3,6-DBSQ)(2) is a high-spin cobalt(II) derivative.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Cheng Ren, Guanghao Ji, Xiankai Li, Jing Zhang
Summary: In this study, a cobalt-catalyzed tail-to-tail hydrodimerization method driven by visible-light photoredox catalysis at ambient temperature was developed. The method is applicable for synthesizing both adipates and adiponitrile and shows high regioselectivity and efficiency.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
D-Y Park, N. Myung
Summary: CoPt and CoPtP thin films were synthesized by direct current aqueous electrodeposition from weak alkaline solutions. The composition of the films was adjusted by varying electrodeposition parameters, resulting in different microstructures and magnetic properties.
FRONTIERS IN CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Luana C. de Camargo, Matteo Briganti, Francielli S. Santana, Danilo Stinghen, Ronny R. Ribeiro, Giovana G. Nunes, Jaisa F. Soares, Enrico Salvadori, Mario Chiesa, Stefano Benci, Renato Torre, Lorenzo Sorace, Federico Totti, Roberta Sessoli
Summary: The study demonstrates that the 17-electron mixed sandwich complex has a remarkable coherence time at low temperatures, making it ideal for surface single-qubit addressing and quantum sensing applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Fabio Santanni, Andrea Albino, Matteo Atzori, Davide Ranieri, Enrico Salvadori, Mario Chiesa, Alessandro Lunghi, Andrea Bencini, Lorenzo Sorace, Federico Totti, Roberta Sessoli
Summary: This study investigates the selection of molecular spin qubits with long coherence time T-m through a combination of theoretical and experimental methods, focusing on the effects of vibrational properties and nuclear spins of hydrogens on spin dynamics. The results show that removing hydrogens can enhance the performance of spin qubits.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Niccolo Giaconi, Andrea Luigi Sorrentino, Lorenzo Poggini, Michela Lupi, Vincent Polewczyk, Giovanni Vinai, Piero Torelli, Agnese Magnani, Roberta Sessoli, Stefano Menichetti, Lorenzo Sorace, Caterina Viglianisi, Matteo Mannini
Summary: The study presents a novel strategy for depositing a sub-monolayer of enantiopure thia[4]helicene radical cations on a pre-functionalized Au(111) substrate, maintaining both the paramagnetic character and the chemical structure of these molecules at the nanoscale. Synchrotron-based X-ray natural circular dichroism confirms the preservation of the handedness of the thia[4]helicene on the surface.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Julia Mayans, Lorenzo Tesi, Matteo Briganti, Marie-Emmanuelle Boulon, Merce Font-Bardia, Albert Escuer, Lorenzo Sorace
Summary: This study reports the synthesis, characterization, structural description, and magnetic and spectroscopic properties of two isostructural molecular magnets based on a chiral ligand. Experimental and theoretical data comparison shows that ab initio calculations are reliable in determining principal values and are crucial for establishing the analysis of EPR and CTM.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Matteo Atzori, Elena Garlatti, Giuseppe Allodi, Simone Chicco, Alessandro Chiesa, Andrea Albino, Roberto De Renzi, Enrico Salvadori, Mario Chiesa, Stefano Carretta, Lorenzo Sorace
Summary: A comprehensive characterization of a 3d organometallic complex is reported, showing its potential for quantum computing applications.
INORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Luca Conti, Alessio Mengoni, Gina Elena Giacomazzo, Lorenzo Mari, Mauro Perfetti, Camilla Fagorzi, Lorenzo Sorace, Barbara Valtancoli, Claudia Giorgi
Summary: The antimicrobial potential of two ruthenium(II) polypyridyl complexes, containing specific polyamine frameworks, was investigated in this study. The complexes showed promising singlet oxygen sensitizing capacities and phototoxicity against gram-positive bacteria, highlighting a versatile tool for enhanced antibacterial strategies.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maja A. Dunstan, Dominic S. Brown, Lorenzo Sorace, Richard A. Mole, Colette Boskovic
Summary: Incorporating lanthanoid(III)-radical magnetic exchange coupling is a possible route to improving the performance of lanthanoid single-molecule magnets, which exhibit slow relaxation and low temperature quantum tunnelling of the magnetization. In this study, Gd(III) complexes were used as model systems to study the Ln-radical exchange coupling. Two new Gd(III)-radical compounds were synthesized, and their structures were confirmed using various characterization techniques. The compounds showed differences in low temperature magnetic properties, with compound 1 exhibiting slow magnetic relaxation in applied magnetic fields and compound 2 relaxing much faster, pointing to the major role of packing effects in modulating slow relaxation of the magnetization.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Anna L. Pellegrino, Claudia Mezzalira, Francesco Mazzer, Lila Cadi Tazi, Andrea Caneschi, Dante Gatteschi, Ignazio L. Fragala, Adolfo Speghini, Lorenzo Sorace, Graziella Malandrino
Summary: In this paper, a series of Dy(hfa)(3)center dot glyme adducts were prepared and the relationship between the coordination framework and magnetic and luminescent properties was investigated.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Walter Giurlani, Martina Vizza, Federico Pizzetti, Marco Bonechi, Matteo Savastano, Lorenzo Sorace, Andrea Stefani, Claudio Fontanesi, Massimo Innocenti
Summary: In this study, magneto-electrochemistry experiments were conducted during the electrodeposition of a ferromagnetic Heusler alloy. The presence of a magnetic field was found to affect the electrochemical measurements and the macroscopic handedness (chirality) of the deposit.
APPLIED SCIENCES-BASEL
(2022)
Article
Chemistry, Inorganic & Nuclear
Elodie Rousset, Matteo Piccardo, Robert W. Gable, Massimiliano Massi, Lorenzo Sorace, Alessandro Soncini, Colette Boskovic
Summary: The photophysical and magnetic properties of lanthanoid ions in both ground and excited states have important applications. Ligand-to-metal charge-transfer (LMCT) states have a substantial impact on these properties, both negatively and positively. However, detecting LMCT states in f-block chemistry, especially in the solid state, remains a challenge. In this study, the LMCT character of the absorption bands in europium compounds was investigated using magnetometry, absorption and emission spectroscopies, and solid-state electrochemistry. The findings suggest a framework for understanding LMCT excited states in lanthanoid compounds in the solid state.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Davide Ranieri, Fabio Santanni, Alberto Privitera, Andrea Albino, Enrico Salvadori, Mario Chiesa, Federico Totti, Lorenzo Sorace, Roberta Sessoli
Summary: We report the synthesis of a new meso-meso (m-m) singly linked vanadyl-porphyrin dimer and its crystallization in two different pseudo-polymorphs. Electron paramagnetic resonance investigation reveals a small but crucial isotropic exchange interaction, J, between the two tilted spin centers. Experimental and DFT studies show a correlation between J values and porphyrin plane tilting angle and distortion. Pulsed EPR analysis demonstrates that the coherence time of the monomer is maintained in the dimers. The spin Hamiltonian parameters identify suitable transitions for computational basis states. These results, combined with the evaporability of porphyrin systems, establish this class of dimers as extremely promising for quantum information processing applications.
Article
Crystallography
Fabio Santanni, Laura Chelazzi, Lorenzo Sorace, Grigore A. Timco, Roberta Sessoli
Summary: Heterotopic ligands with chemically different binding centers are used to obtain heteronuclear metal complexes with different paramagnetic centers. This molecular approach has the potential to yield multi-spin adducts for quantum information processing. This study reports the structural and magnetic characterization of a novel adduct {Cr(pybd)(3)[Cu(cyclen)](2)}(BF4)(4), which demonstrates weak magnetic couplings and maintains distinctive EPR signals for Cr3+ and Cu2+ moieties.
Article
Chemistry, Multidisciplinary
Davide Ranieri, Alberto Privitera, Fabio Santanni, Karolina Urbanska, Grant J. Strachan, Brendan Twamley, Enrico Salvadori, Yu-Kai Liao, Mario Chiesa, Mathias O. Senge, Federico Totti, Lorenzo Sorace, Roberta Sessoli
Summary: By synthesizing and studying a VIVO-CuII porphyrin dimer, we observed measurable exchange coupling and good spin coherence, making it suitable for operating two-qubit molecular spin-based quantum gates under various conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Manuel Imperato, Alessio Nicolini, Marco Borsari, Matteo Briganti, Mario Chiesa, Yu-Kai Liao, Antonio Ranieri, Arsen Raza, Enrico Salvadori, Lorenzo Sorace, Andrea Cornia
Summary: We investigated the performance of heterobimetallic lantern complexes [PtVO(SOCR)4] as charge neutral electronic qubits based on vanadyl complexes. The results showed that these complexes exhibit good spin coherence properties, making them suitable for applications in materials science and quantum technologies.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Simone Chicco, Alessandro Chiesa, Giuseppe Allodi, Elena Garlatti, Matteo Atzori, Lorenzo Sorace, Roberto De Renzi, Roberta Sessoli, Stefano Carretta
Summary: The research demonstrates that [VO(TPP)] is a promising system for implementing quantum computation algorithms based on encoding information in multi-level units, with applications in quantum error correction and simulation.