Article
Chemistry, Inorganic & Nuclear
Lixi Feng, Yue Yang, Yu-Xia Wang, Yizhen Zhao, Zhong-Yi Liu, Junzhuang Cong, Yi-Quan Zhang, Peng Cheng
Summary: We report a method for synthesizing single-molecule magnets through a single-crystal to single-crystal transformation. This process yields two single-molecule magnets with similar triangular Dy3 cores but distinct solvents and space groups achieved via solvent exchange. The magnetic properties reveal that both Dy3 molecules have similar toroidal moments but exhibit diverse multiple magnetization dynamic behaviors due to the influence of spin-lattice coupling from different solvent molecules. Single-crystal to single-crystal transformation by solvent exchange provides a new way to study magneto-structural relationships in single-molecule magnets.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jerome Long, Aleksei O. Tolpygin, Ekaterina Mamontova, Konstantin A. Lyssenko, Dan Liu, Munirah D. Albaqami, Liviu F. Chibotaru, Yannick Guari, Joulia Larionova, Alexander A. Trifonov
Summary: A new octahedral luminescent Single-Molecule Magnet (SMM) with massive crystal-field splitting and an anisotropic barrier of 1385 cm(-1) is reported, with a unique mechanism behind the high blocking barrier revealed through magnetic measurements and ab initio analysis. The novel mechanism involves quenching of one-phonon transitions between low-lying crystal-field multiplets, forcing relaxation to proceed through a fourth doublet. The short relaxation time observed is attributed to non-axial anisotropy and tunnelling relaxation path via interaction with nuclear spins.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Yidian Wang, Qian-Cheng Luo, Yuan-Qi Zhai, Peng-Bo Jin, Zhendong Fu, Qi Sun, Fan-Ni Li, Yan-Zhen Zheng
Summary: In this study, two dysprosium(III) single-molecule magnets (SMMs) were synthesized using a pseudoallyl ligand and pentamethylcyclopentadienyl. The SMMs exhibited distinct energy barriers.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Multidisciplinary
Yidian Wang, Qian-Cheng Luo, Yuan-Qi Zhai, Peng-Bo Jin, Zhendong Fu, Qi Sun, Fan-Ni Li, Yan-Zhen Zheng
Summary: In this study, two dysprosium(III) single-molecule magnets (SMMs) were prepared using a pseudoallyl ligand, N,N'-chelating amidinate (Am), and pentamethylcyclopentadienyl (Cp*). The obtained SMMs, [{(AmiPr)-DyCp*(mu-Cl)}2] and [AmdippDyCp*(Cl)(mu-Cl)Li(THF)3], exhibited distinct energy barriers (Ueff) of 97 and 472 K, respectively, with the latter value similar to a homoleptic Cp*-based Dy-SMM.
CRYSTAL GROWTH & DESIGN
(2022)
Review
Chemistry, Inorganic & Nuclear
Roman Boca, Cyril Rajnak
Summary: Slow magnetic relaxation is a common feature in magnetic materials, with the relaxation time determined by high spin reversal barriers and molecular spin. Recent experimental data has shown slow magnetic relaxation in systems with positive, small or negligible D. Some materials exhibit multiple relaxation channels.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Biochemistry & Molecular Biology
Susanta Hazra, Cyril Rajnak, Jan Titis, M. Fatima C. Guedes da Silva, Roman Boca, Armando J. L. Pombeiro
Summary: The reaction of Schiff base N,N'-ethylene bis(salicylaldimine), CoCl2·6H2O, and [Ph2SnCl2] in acetone produces a mixed valence compound. The structural features of the resulting organometallic systems are dependent on the solvent used. Compound 1 exhibits slow magnetic relaxation behavior and is classified as a single molecule magnet.
Article
Chemistry, Multidisciplinary
Chunyang Zhang, Mengyao Liu, Xingwei Cai, Lei Chen, Yuan-Zhong Liu, Huihui Cui, Shao-Liang Zhang, Aihua Yuan
Summary: A mononuclear six-coordinate Dy-III complex with an octahedral coordination environment has been synthesized, exhibiting field-induced slow magnetic relaxation with an energy barrier of 21.3 K, providing a rare case for mononuclear octahedral Ln-based complexes with slow magnetic relaxation behavior.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Tomasz Charytanowicz, Robert Jankowski, Mikolaj Zychowicz, Szymon Chorazy, Barbara Sieklucka
Summary: This study reports an efficient method to generate slow magnetic relaxation in bimetallic coordination chains and to modify them into single-chain magnets. The modification of the coordination chains leads to different magnetic properties.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Inorganic & Nuclear
Jin-Hua Wang, Zhao-Yang Li, Masahiro Yamashita, Xian-He Bu
Summary: This article explores the latest developments in novel functional molecular-based magnetic materials, focusing on cyano-bridged transition-metal-based single-molecule magnets and single-chain magnets research. The review mainly discusses the construction of different molecular-magnetic materials based on the cyanide ligand's strong affinity for transition metals. Key topics include structural topologies, SMMs, SCMs, and important principles for constructing diverse magnetic materials.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Xiaoshuang Gou, Ning Liu, Yuewei Wu, Wenlong Lan, Mengmeng Wang, Wei Shi, Peng Cheng
Summary: In this study, a light-induced substance conversion system using an Er(iii) coordination polymer and its Y(iii)-diluted analogue was reported. The transformed products exhibited higher T-XM values and lower effective energy barriers for magnetization reversal compared to the untransformed compounds. This work not only provides a new light-conversion system, but also reveals the nature of photo-induced variation of magnetic properties.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Ming Liu, Xiao-Han Peng, Fu-Sheng Guo, Ming-Liang Tong
Summary: Significant progress has been made in single-molecule magnets (SMMs) in recent years, with the milestone achievement of hysteresis blocking temperature surpassing the boiling point of liquid nitrogen. Although our understanding of constructing high-performance rare-earth SMMs has improved, there are few successful SMMs reported for actinides that possess stronger spin-orbital coupling. The review summarizes the progress on actinide SMMs and examines potential future directions.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Inorganic & Nuclear
Cyril Rajnak, Roman Boca
Summary: The thermal behavior of some mononuclear transition metal and lanthanide complexes shows a non-traditional pattern where the relaxation time at low temperatures shortens instead of prolonging. The relaxation time in the low-temperature range can be recovered using equations and processes involving phonon bottleneck and unusual behavior.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Ruirui Wang, Binling Yao, Feifei Bai, Wen Wang, Licun Li, Yue Ma, Qinglun Wang, Bin Zhao, Yuanzhu Zhang
Summary: Two isostructural mononuclear lanthanide complexes were synthesized by solvothermal reaction. Magnetic measurements revealed unique magnetization relaxation processes in the Dy-III complex, indicating a field-induced single-ion magnet behavior. The magneto-structural correlation was further discussed based on an electrostatic model calculation.
Article
Chemistry, Inorganic & Nuclear
Selvakumar Arumugam, Bjoern Schwarz, Prathap Ravichandran, Sunil Kumar, Liviu Ungur, Kartik Chandra Mondal
Summary: This work investigates the dynamic magnetic properties of a complex [(Cp-Ar3)(4)(Dy2Cl4K2)-Cl-III]& BULL;3.5(C7H8) synthesized using a tri-aryl-substituted cyclopentadienyl ligand (Cp-Ar3). The Dy(III)-metallocene weakly couples via K2Cl4 and exhibits slow relaxation of magnetization below 14.5 K under zero applied dc field through KD3 energy levels with an energy barrier of 136.9/133.7 cm(-1) at the Dy sites. The coordination of two chloride ions at each Dy centre leads to geometrical distortion and reduction of the single-ion axial anisotropy energy barrier.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Kristina A. Smirnova, Yulia O. Edilova, Mikhail A. Kiskin, Artem S. Bogomyakov, Yulia S. Kudyakova, Marina S. Valova, Galina V. Romanenko, Pavel A. Slepukhin, Victor I. Saloutin, Denis N. Bazhin
Summary: Functionalized perfluoroalkyl lithium beta-diketonates (LiL) react with lanthanide(III) salts (Ln = Eu, Gd, Tb, Dy) in methanol to give heterobimetallic Ln-Li complexes. The crystal packing of the complexes is influenced by the length of fluoroalkyl substituent in the ligand. The photoluminescent and magnetic properties of the heterobimetallic beta-diketonates in the solid state are reported, along with the effect of coordination environment on their luminescent properties and single-ion magnet behavior.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Shen Zhou, Jiayue Yuan, Zi-Yu Wang, Kun Ling, Peng-Xiang Fu, Yu-Hui Fang, Ye-Xin Wang, Zheng Liu, Kyriakos Porfyrakis, G. Andrew D. Briggs, Song Gao, Shang-Da Jiang
Summary: The addressability of individual electron spin levels in endohedral nitrogen fullerenes has been achieved using molecular engineering and liquid-crystal-assisted methods. This allows for the coherent manipulation of electron spin levels and the implementation of quantum geometric phase manipulation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Oleh Stetsiuk, Leo La Droitte, Violaine Goudy, Boris Le Guennic, Olivier Cador, Gregory Nocton
Summary: The article reports the synthesis and structural characterization of a series of Ln(C9H9)(3) complexes with the cyclononatetraenyl (Cnt, C9H9) ligand (Ln = Y, Gd, Tb, Dy, Ho, Er, Tm). The X-ray diffraction studies on the complexes reveal that the Cnt ligand adopts a bent conformation to accommodate its large size while maintaining its aromaticity. The magnetic behavior of the complexes is consistent with trivalent lanthanide ions, and computational analysis confirms the trivalent electronic structure.
Article
Chemistry, Multidisciplinary
Yu-Hui Fang, Zheng Liu, Shen Zhou, Peng-Xiang Fu, Ye-Xin Wang, Zi-Yu Wang, Zhe-Ming Wang, Song Gao, Shang-Da Jiang
Summary: This study demonstrates for the first time the feasibility of achieving quantum coherent SEC effect in molecular ferroelectrics by manipulating the zero-field splitting of Mn(II) ions to achieve controllable phase shifts. Detailed investigations reveal the vanishment and enhancement of SEC effects at different crystal orientations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Sitthichok Kasemthaveechok, Laura Abella, Marion Jean, Marie Cordier, Nicolas Vanthuyne, Thierry Guizouarn, Olivier Cador, Jochen Autschbach, Jeanne Crassous, Ludovic Favereau
Summary: We report a new molecular design for persistent chiral organic open-shell systems, which exhibit configurational stability and an inversion in energy of the singly occupied molecular orbital (SOMO) and the highest doubly occupied molecular orbital (HOMO). The designed extended helical pi-conjugated systems with delocalized unpaired electron resonance play a crucial role in achieving chemical stabilities, which is different from the traditional steric protection approach. The obtained helical monoradicals show unique features that allow for the exploration of chiral intramolecular electron transfer (IET) process in solvents of different polarity, resulting in unprecedented electronic circular dichroism (ECD) sign inversion for radical transitions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Xiao-Xiang Chen, Jia-Tong Li, Yu-Hui Fang, Xin-Yu Deng, Xue-Qing Wang, Guangchao Liu, Yunfei Wang, Xiaodan Gu, Shang-Da Jiang, Ting Lei
Summary: This study reports three high-mobility semiconducting polymers with different spin ground states. The researchers demonstrate that polymer building blocks with small singlet-triplet energy gap could increase the diradical character in copolymers. The electronic structure, spin density, and solid-state interchain interactions are crucial for the ground states of the high-spin polymers.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Luca Muenzfeld, Milena Dahlen, Adrian Hauser, Nolwenn Mahieu, Senthil Kumar Kuppusamy, Jules Moutet, Maxime Tricoire, Ralf Koeppe, Leo La Droitte, Olivier Cador, Boris Le Guennic, Gregory Nocton, Eufemio Moreno-Pineda, Mario Ruben, Peter W. Roesky
Summary: The solvation of [(CNT)Ln(eta(8)-COT)] complexes with tetrahydrofuran (THF) can lead to neutral and ionic species in a solid-to-solid transformation. These species exhibit switchable luminophores and single-molecule magnet properties due to the distortion caused by solvation. The desolvation of the coordinated solvents can be achieved through a dynamic vacuum or temperature gradient stimulus. Raman spectroscopic investigations confirm the fast and reversible solvation and desolvation processes, and a Nd:YAG laser is found to induce a spatially resolved self-sufficient switching process for the Ce(III) analogue.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kais Dhbaibi, Maxime Grasser, Haiet Douib, Vincent Dorcet, Olivier Cador, Nicolas Vanthuyne, Francois Riobe, Olivier Maury, Stephan Guy, Amina Bensalah-Ledoux, Bruno Baguenard, Geert L. J. A. Rikken, Cyrille Train, Boris Le Guennic, Matteo Atzori, Fabrice Pointillart, Jeanne Crassous
Summary: The combination of physical properties sensitive to molecular chirality in a single system allows the observation of interesting phenomena such as magneto-chiral dichroism (MChD) and circularly polarized luminescence (CPL), which have potential applications in optical data readout and display technology. By coordinating a chiral organic chromophore to Yb(hfac)(3) units, homochiral one-dimensional coordination polymers of Yb-III were designed, which exhibit strong magnetic anisotropy and show single-molecule magnet behavior and room temperature magneto-chiral dichroism (MChD). Computational investigations support the correlation between MChD and the structure.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Moritz Bernhardt, Maciej D. D. Korzynski, Zachariah J. J. Berkson, Fabrice Pointillart, Boris Le Guennic, Olivier Cador, Christophe Coperet
Summary: Generating or retaining slow magnetic relaxation in surface-immobilized single-molecule magnets (SMMs) from molecular precursors is a challenging task. However, a material with SMM characteristics has been successfully generated by chemisorption of (Cp-ttt)(2)DyCl on a silica surface containing tailored Lewis acidic Al-(III) sites. Detailed studies reveal slow magnetic relaxation up to 51 K, hysteresis up to 8 K, and an effective energy barrier (U (eff)) of 449 cm(-1), the highest reported for a supported SMM.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Multidisciplinary
Carlo Andrea Mattei, Vincent Montigaud, Bertrand Lefeuvre, Vincent Dorcet, Gilles Argouarch, Olivier Cador, Boris Le Guennic, Olivier Maury, Claudia Lalli, Yannick Guyot, Stephan Guy, Cyprien Gindre, Amina Bensalah-Ledoux, Francois Riobe, Bruno Baguenard, Fabrice Pointillart
Summary: Lanthanide ions have attracted significant interest due to their optical and magnetic properties. The combination of single-molecule magnet (SMM) behavior and circularly polarized luminescence (CPL) in a single molecular system is rare and deserves attention for the design of multifunctional materials. Chiral one-dimensional coordination compounds involving Yb(iii) center and BINOL-derived bisphosphate ligands exhibited field-induced SMM behavior and near infrared CPL in the solid state, as characterized by X-ray diffraction.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Review
Chemistry, Multidisciplinary
Fabrice Pointillart, Kevin Bernot, Boris Le Guennic, Olivier Cador
Summary: This review article provides a comprehensive description of the influence of nuclear spin, namely the hyperfine interaction, on the magnetic properties of lanthanide single-molecule magnets (SMMs) and on quantum information processing of qudit. The article analyzes this influence for non-Kramers and Kramers lanthanide SMMs, as well as for the electronic distribution of the electron in 4f orbitals, i.e. oblate and prolate ions. Additionally, the role of magnetic interactions in isotopically enriched polynuclear Dy(iii) SMMs is discussed, along with the possible effect of superhyperfine interaction due to the nuclear spin of elements surrounding the lanthanide centre. The effect of nuclear spin on the dynamics of lanthanide SMMs is demonstrated using various techniques such as magnetometry, muon spectroscopy, and Mossbauer and Resonance Vibrational Spectroscopies.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Hao Wang, Zhenhua Zhu, Leo La Droitte, Wuping Liao, Olivier Cador, Boris Le Guennic, Jinkui Tang
Summary: Two luminescent Tb(iii)-calixarene aggregates with architectures of 1D chain (1) and 3D network (2) have been synthesized, and their single-molecule toroidal (SMT) characteristics have been experimentally investigated with the support of ab initio calculations. Aggregate 2 with a 3D structure is the first covalently bonded 3D SMT polymer that has been successfully synthesized.
Article
Chemistry, Multidisciplinary
Florian Benner, Leo La Droitte, Olivier Cador, Boris Le Guennic, Selvan Demir
Summary: A judicious combination of radical ligands with paramagnetic metal ions elicits strong magnetic exchange coupling, which leads to important properties for future technologies. The metal-radical approach aids in effective magnetic communication, especially for lanthanide ions. The presented complexes of bisbenzimidazole-based dilanthanide exhibit strong antiferromagnetic coupling and single-molecule magnetism, showing potential for applications in organic radical bridge materials.
Article
Chemistry, Multidisciplinary
Ziqi Zhu, Di Zhang, Tongtong Xiao, Yu-Hui Fang, Xiao Xiao, Xiao-Ge Wang, Shang-Da Jiang, Dahui Zhao
Summary: This study presents a convenient method for integrating stable high-spin radicals into (hetero)aromatic polycycles, forming stable carbon-based polyradicals. The properties of the newly designed polycycles were thoroughly characterized, and a general method for installing stable polyradicals into functional pi-systems was proposed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Maciej Damian Korzynski, Moritz Bernhardt, Vladyslav Romankov, Jan Dreiser, Guy Matmon, Fabrice Pointillart, Boris Le Guennic, Olivier Cador, Christophe Coperet
Summary: In this study, a family of organometallic rare-earth complexes with different magnetic behaviors was reported by introducing different ligands. Compared to previous research, the complexes in this study exhibited a simplified magnetic relaxation behavior, and a mononuclear derivative of early-lanthanide complex was successfully prepared.
Article
Chemistry, Inorganic & Nuclear
Pawan Kumar, Jessica Flores Gonzalez, Prem Prakash Sahu, Naushad Ahmed, Joydev Acharya, Vierandra Kumar, Olivier Cador, Fabrice Pointillart, Saurabh Kumar Singh, Vadapalli Chandrasekhar
Summary: The synthesis, structure, and magnetism of four tetranuclear complexes have been reported, with two peroxide ligands assisting in their formation. Weak intramolecular antiferromagnetic interactions were found in three of the complexes, while a structural change in the fourth complex led to a ferromagnetic interaction. The magnetothermal behavior of one complex displayed a magnetocaloric effect with a maximum entropy change close to the calculated value.
INORGANIC CHEMISTRY FRONTIERS
(2022)
