Article
Chemistry, Multidisciplinary
Chen Zhao, Zhenhua Zhu, Jinjiang Wu, Qianqian Yang, Tesfay Gebretsadik Ashebr, Xiao-Lei Li, Jinkui Tang
Summary: Two pairs of chiral end-on azido-bridged dinuclear hexaazamacrocycles were synthesized by adjusting the molar ratio of reactants, and their magnetic properties were studied. One of the compounds exhibited single-molecule magnet behavior under zero dc field, showing potential applications in the field of magnetism.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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)
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)
Review
Chemistry, Inorganic & Nuclear
Andoni Zabala-Lekuona, Jose Manuel Seco, Enrique Colacio
Summary: The discovery of Single-Molecule Magnets in 1993 revolutionized the field of information storage by shrinking the size of bits to molecular levels. Despite initially operating at temperatures near absolute zero, collaboration between chemists and physicists have led to the development of materials that can operate above liquid nitrogen temperatures. The evolution of SMMs has involved the study of various routes towards high performance materials, with each route essential for understanding the quantum dynamics behind these molecules.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Tian Han, You-Song Ding
Summary: A complex with a dysprosium ion coordinated by two bulky chelating silyldiamide ligands was synthesized and characterized. The coordination geometry allowed slow magnetic relaxation up to 42 K, making it the first silyldiamido dysprosium single-molecule magnet.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Maria Brzozowska, Gabriela Handzlik, Mikolaj Zychowicz, Dawid Pinkowicz
Summary: By using the chelating blocking ligand (N3N)(3-) with large steric -SiMe3 groups, the Dy-2 complex exhibits slow magnetic relaxation typical of single molecule magnets. Furthermore, magnetic studies reveal weak antiferromagnetic interactions in the Gd-2 complex, suggesting similar interactions in Dy-2, which may be responsible for its unique SMM behavior and lack of magnetic hysteresis loop.
Article
Chemistry, Inorganic & Nuclear
Xiu-Fang Ma, Ying Guo, Xin-Da Huang, Ge-Hua Wen, Song-Song Bao, Yi-Quan Zhang, Li-Min Zheng
Summary: Three rare earth complexes were reported in this study, with two of them showing distinct magnetic dynamics and luminescence properties as polymorphs.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Yue Cheng, Qi Liu, Zi-Yi Chen, Yuan-Zhu Zhang
Summary: The treatment of CoCl2 center dot 6H(2)O and tris(pyrazolyl-1-yl)borate tricyanoiron(III) anions at an elevated temperature resulted in two less-common pearl-chain-like compounds. Compound 1 exhibited typical single-chain magnet behavior with an effective energy barrier of 28.0 K, while compound 2 did not show Glauber dynamics despite their similar structures. Changes in the local coordination environments of cobalt ions and cyanide linkages were identified as contributing factors to the significant difference in their magnetic properties.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Fabrice Pointillart, Jessica Flores Gonzalez, Haiet Douib, Vincent Montigaud, Charles J. McMonagle, Boris Le Guennic, Olivier Cador, Dawid Pinkowicz, Michael R. Probert
Summary: The extreme sensitivity of trivalent lanthanide ions to crystal field variations leads to the emergence of single-molecule magnetic switching under various stimuli. Pressure can be used as an external stimulus to finely tune the magnetic modulation of single-molecule magnets, instead of traditional methods like light irradiation or chemical reactions. Experimental investigation of a well-known single-molecule magnet under high applied pressures demonstrated reversible piezo-chromic properties and pressure modulation of slow magnetic relaxation behavior, which were supported by ab initio calculations. The magnetic study of a diluted sample indicated that variations in the electronic structure mainly have an intermolecular origin with weak intramolecular contribution.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Hai-Ling Wang, Ju -Fen Ai, Yu-Feng Wang, Shui Yu, Yun-Lan Li, Zhong-Hong Zhu, Hua-Hong Zou
Summary: This study successfully constructed two binuclear dysprosium complexes with different single-molecule magnet (SMM) properties and cluster core connections through solvothermal in situ reactions. Magnetic studies showed that these complexes exhibited field-induced SMM behaviors.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Multidisciplinary
Michal Liberka, Mikolaj Zychowicz, Wiktor Zychowicz, Szymon Chorazy
Summary: This method efficiently generates magnetic anisotropy of Dy-III centers by inserting aromatic N-oxide ligands on labile axial positions, providing a novel and convenient route to rationally designed single-molecule magnets.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Bertrand Lefeuvre, Thierry Guizouarn, Vincent Dorcet, Marie Cordier, Fabrice Pointillart
Summary: The reaction between the ligand (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide (H(2)opch) and the metallo-precursor [Dy(hfac)(3)].2H(2)O resulted in the formation of a homometallic coordination complex [Dy-2(hfac)3(H2O)(Hopch)(2)][Dy(hfac)(4)] (1). Addition of both [Dy(hfac)(3)] 2H(2)O and Fe(II) salt produced the heterobimetallic tetranuclear complex [FeDy3(hfac)(8)(H2O)(2)(opch)(2)] (2), while addition of the co-ligand 1,2-Bis(2-hydroxy-3-methoxybenzylidene) hydrazine (H(2)bmh) led to the formation of two heterobimetallic tetranuclear complexes [Fe3Dy(hfac)(6)(opch)(2)(H(2)bmh)] C6H14 (3) C6H14 and [Fe2Dy2(hfac)(7)(opch)(2)(H(2)bmh)] 0.5C(7)H(16) (4). Single crystal X-ray diffraction and dc magnetic investigation confirmed the involvement of iron centers in different oxidation states in compounds 3 and 4. Dynamic magnetic measurements revealed the single-molecule magnet behavior of compounds 1 and 2 primarily due to the presence of ferromagnetic interactions.
Article
Chemistry, Inorganic & Nuclear
Dong Shao, Wan-Jie Tang, Zhijun Ruan, Xiaodong Yang, Le Shi, Xiao-Qin Wei, Zhengfang Tian, Kusum Kumari, Saurabh Kumar Singh
Summary: We report the design and synthesis of a one-dimensional Dy(iii) coordination polymer that exhibits reversible structural transformation and controlled magnetic and proton conduction properties. This new coordination compound can undergo single-crystal-to-single-crystal transformation during the desorption/adsorption of water molecules, resulting in changes in magnetic properties and proton transport pathways. The results not only provide the first example of controlled single-ion magnetism and proton conduction behavior in Dy(iii) sulfonates but also demonstrate the potential of using water molecules to dynamically control magnetic and electrical properties.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Maciej D. Korzynski, Zachariah J. Berkson, Boris Le Guennic, Olivier Cador, Christophe Coperet
Summary: Single-molecule magnets (SMMs) offer unmatched information storage density, potential applications in quantum computing and spintronics, and are mainly organometallic lanthanide complexes. However, the challenge lies in surface immobilization due to the sensitivity of magnetic properties to changes in electronic structure. This study successfully identifies siloxides on partially dehydroxylated silica surface as suitable replacements for typical ligand architectures, leading to a significant increase in magnetization relaxation times.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Qianqian Yang, Liviu Ungur, Liviu F. Chibotaru, Jinkui Tang
Summary: This study reveals a toroidal arrangement of the magnetic moment in a tetrahedral Dy-4 complex, rather than centripetal anisotropies.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Matthias Tombers, Jennifer Meyer, Jonathan Meyer, Arkadiusz Lawicki, Vicente Zamudio-Bayer, Konstantin Hirsch, J. Tobias Lau, Bernd von Issendorff, Akira Terasaki, Thomas A. Schlathoelter, Ronnie A. Hoekstra, Sebastian Schmidt, Annie K. Powell, Eva Kessler, Marc H. Prosenc, Christoph van Wuellen, Gereon Niedner-Schatteburg
Summary: In this study, the magnetic properties of isolated cationic species [Mn12O12(CH3COO)(15)(CH3CN)](+) were investigated using gas phase X-ray Magnetic Circular Dichroism spectroscopy, and found to resemble closely to that of the corresponding bulk samples. Additionally, broken symmetry DFT calculations revealed that the Mn-4(IV) core exhibits almost no magnetic anisotropy, while the surrounding Mn-8(III) ring is highly anisotropic. These intrinsic magnetic properties are largely unaffected by environmental factors, suggesting robustness in the Mn-12 core scaffold within these complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Hanna E. Wagner, Nils Frank, Elham Barani, Christopher E. Anson, Lea Bayer, Annie K. Powell, Karin Fink, Frank Breher
Summary: This study describes the synthesis and characterization of novel 1,1'-difunctionalized ferrocene metalloligands. The functionalization of one cyclopentadienyl ring with different aryl moieties and the reaction with various metals yielded corresponding complexes. The electrochemical behavior of the ligands and complexes was investigated, and the influence of functional groups on the reaction of complexes was confirmed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
S. Sold, B. C. Mummaneni, N. C. Michenfelder, Y. Peng, A. K. Powell, A-N Unterreiner, G. Lefkidis, W. Huebner
Summary: This study combines experimental and theoretical methods to investigate the ultrafast transient absorption spectroscopy of a unique compound in DMF, shedding light on its optical properties and relaxation processes on different timescales. Theoretical simulations use cutting-edge quantum chemistry techniques to extract relaxation times from first principles and provide insights into the compound's behavior under laser pulses and relaxation processes.
Article
Chemistry, Inorganic & Nuclear
Qianqian Yang, Liviu Ungur, Wolfgang Wernsdorfer, Jinkui Tang
Summary: This study presents the synthesis and characterization of a series of Tb-4 SMTs isolated from reduced or dimerized Schiff base ligands. These complexes share a similar mu(4)-O bridged Tb-4 square core and exhibit diamagnetic ground states. Micro-SQUID technique was used to investigate the magnetic moments, revealing a toroidal arrangement. Ab initio calculations confirm the mixed-moment SMT properties of these complexes, providing a new strategy for generating single molecule toroics in terbium-based molecules.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Thomas Ruppert, Soeren Schlittenhardt, Nithin Suryadevara, Olaf Fuhr, Christopher E. Anson, Mario Ruben, Annie K. Powell
Summary: Four new heterometallic trinuclear complexes were synthesized and analyzed, revealing the variation of M-Dy-M angles and M···M distances with different metal M. Magnetic susceptibility measurements showed ferromagnetic interactions between Co-II and Cu-II at low temperatures.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Editorial Material
Chemistry, Multidisciplinary
[Anonymous]
Article
Chemistry, Physical
Nicolas Schork, Masooma Ibrahim, Ananya Baksi, Steffen Kraemer, Annie K. Powell, Gisela Guthausen
Summary: Selectivity and image contrast in magnetic resonance imaging (MRI) are challenging and can be addressed by contrast agents. The relaxation properties of these agents, specifically the paramagnetic relaxation enhancement (PRE), need to be understood and improved. This study focused on the H-1-relaxivities of high-spin heterometallic clusters and investigated the effects of rotational and diffusion correlation times as well as solvent viscosity on relaxivities. The variation of lanthanide and transition-metal ions in the clusters also provided insights into the sensitivity of PRE to electron spin properties and cooperative effects.
Article
Chemistry, Multidisciplinary
Xiang Zhong, Zhao-Bo Hu, Tong-Kai Luo, Yan Peng, Sui-Jun Liu, Christopher E. Anson, Annie K. Powell, He-Rui Wen
Summary: Three one-dimensional Ln(III) complexes based on hydrazone Schiff-base ligands were reported. The Dy-III analogue exhibited a field-induced SMM behavior with U (eff) = 43 K, while the Gd-III analogue showed a significant magnetic thermal effect with a maximum -ΔS(m) value of 21.32 J kg(-1) K-1 at 3 K and 7 T. The structures of the complexes were also characterized. The SMM behavior in the Dy-III compound was attributed to its single-ion properties, which was confirmed by comparing it with the Y/Dy diluted complex. On the other hand, the magnetocaloric effect in the Gd-III analogue was observed, with a maximum entropy change -ΔS(m) of 21.32 J kg(-1) K-1 at ΔH = 7 T and 3 K.
CRYSTAL GROWTH & DESIGN
(2023)
Review
Chemistry, Multidisciplinary
Veacheslav Vieru, Silvia Gomez-Coca, Eliseo Ruiz, Liviu F. Chibotaru
Summary: This review discusses the synthesis methods of single-molecule magnets (SMMs) and the basic factors affecting their performance, as well as the strategies for further enhancing SMM performance. Practical approaches for designing SMMs for memory devices are also presented.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Naoya Iwahara, Liviu F. Chibotaru
Summary: The synergistic interplay of different interactions in materials leads to the emergence of novel quantum phenomena. Spin-orbit and vibronic couplings usually counteract each other; however, in cubic d(1) double perovskites they coexist and give rise to spin-orbit-lattice entanglement with unquenched dynamic Jahn-Teller effect on the metal sites. The correlation of these entangled states induced by intersite interactions has not been assessed so far.
Article
Chemistry, Inorganic & Nuclear
Dan Liu, Xuefeng Guo, Xiaoyong Zhang, Abdullah A. Al-Kahtani, Liviu F. Chibotaru
Summary: In this study, the single-molecule magnet (SMM) behavior of a series of lanthanide ions (Tb3+, Dy3+, Ho3+, Er3+, Tm3+ and Yb3+) encapsulated in zigzag carbon nanotubes (CNTs) of different diameters was investigated ab initio. The results showed that, except for Er3+ encapsulated in the (7,0) CNT, none of the investigated systems exhibited any blocking behavior. This can be attributed to the strong competition between axial and equatorial contributions to the crystal field of the encapsulated ions, resulting in weak or lack of magnetic axiality. These results provide useful theoretical guidance for the design of high-performance SMMs via modulating the crystal field of the ligand environment.
DALTON TRANSACTIONS
(2023)
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
Chemistry, Multidisciplinary
Xiao-Lei Li, Lang Zhao, Jianfeng Wu, Wei Shi, Niklas Struch, Arne Luetzen, Annie K. Powell, Peng Cheng, Jinkui Tang
Summary: In situ metal-templated (hydrazone) condensation of 4,6-dihydrazino-pyrimidine, o-vanillin, and dysprosium ions resulted in the formation of discrete hexa- or dodecanuclear metallosupramolecular Dy-6(L)(6) or Dy-12(L)(8) aggregates. The structures exhibited unique circular helical or tetragonal bipyramid architectures, and the coordination mode of the bis(hydrazone) ligand L varied depending on the complex. The formation of the aggregates could be controlled by adjusting the reaction conditions. Dy-6(L)(6) showed a significant spin-relaxation energy barrier of 435 K, making it a promising candidate for lanthanide single-molecular magnets.
Article
Chemistry, Inorganic & Nuclear
Maolin You, Giang T. Nguyen, Dong Shao, Te Wang, Xiao-Yong Chang, Liviu Ungur, Yuan-Zhu Zhang
Summary: This study successfully manipulates the transition temperature of spin-crossover complexes through different synthetic strategies, providing new insights for the development of molecular magnetism.
DALTON TRANSACTIONS
(2022)
