2024
197. Air and Thermally Stable Fluoride Bridged Rare-Earth Clusters Showing Intense Photoluminescence and Potential LED Application
Jian-Yue He, Yu Wang, Xi Chen, Wei-Peng Chen, Guijiang Zhou, Yan-Zhen Zheng*
Adv. Mater. 2024, 2406882. DOI: 10.1002/adma.202406882. Link
Highlight: 氟化物基晶格能够有效减少稀土基发光材料声子猝灭。这里,我们引入了氟离子,并采用“混配体”策略,通过简单的一锅法获得了一类具有纳米尺寸、空气和热稳定性的稀土(RE)团簇晶体RE16(μ4-F)6(μ3-F)12(tBuCOO)18[N(CH2CH2O)3]4 (RE = Eu, EuFC-16;RE = Tb, TbFC-16)。这两种团簇展现出高的量子产率、色纯度、疏水性以及溶解度。作为发光涂层材料,它们在荧光粉转换发光二极管(pc-LED)中具有极大地潜力,封装得到的LED器件展现出高的发光亮度、高的显色指数,可调的色温以及优异的防水能力。
196. Exploring the Magnetism of C5/C2B3 Heteroleptic Organolanthanide Sandwiches
Ye-Ye Liu, Qian-Cheng Luo, Peng-Bo Jin, Yan-Zhen Zheng*
Chin. J. Chem. 2025, 43, 131. DOI: doi.org/10.1002/cjoc.202400730. Link
195. Equatorial aminopyridine ligands stabilize an unusual straightly bridging mode in dimeric dysprosium(III) single-molecule magnets
Qian-Cheng Luo#, Xia-Li Ding#, Wen-Jie Xu#, Yuan-Qi Zhai, Yan-Zhen Zheng*
Chin. Chem. Lett. 2024, DOI: 10.1016/j.cclet.2024.110304. Link
194. Polymeric Manganese(II) Acetate Derivatives: Syntheses, Crystal Structures and Magnetic Properties
Dong-Yang Li, Xiao-Nan Zhang, Wei-Peng Chen*, Yuan-Qi Zhai, Yan-Zhen Zheng*
Eur. J. Inorg. Chem. 2024, 27, e2024003. DOI: 10.1002/ejic.202400360. Link
193. Enhancing blocking temperature using inverse hydrogen bonds for non-radical bridged dimeric Dy(III) single-molecule magnets
Peng-Bo Jin#, Qian-Cheng Luo#, Ye-Ye Liu, Yan-Zhen Zheng*
Sci. China Chem 2024. DOI: 10.1007/s11426-024-2157-7. Link
192. Organolanthanide Single-Molecule Magnets with Heterocyclic Ligands
Yidian Wang, Qian-Cheng Luo, Yan-Zhen Zheng*
Angew. Chem. Int. Ed. 2024, e202407016. DOI: 10.1002/anie.202407016. Link
191. Effect of Mn2+ Doping on the Photoluminescence of Hybrid One-Dimensional Lead Halide Post-Perovskites
Faizan Ahmad, Mohamed Saber Lassoued*, Wei-Peng Chen, Gao-Yang Gou, and Yan-Zhen Zheng*
ACS Appl. Mater. Interfaces. 2024, article accepted. DOI: 10.1021/acsami.4c03070. Link
190. A New Family of SO42– -Templated 3d-4f High-Nuclearity Clusters: Syntheses, Structures, and Magnetic Properties
Caihong Fan, Kaipeng Bai, Qiancheng Luo, Tian Han,* Chang Huang, Yanzhen Zheng, and Weipeng Chen*
Chin. J. Chem. 2024, 42, 2438-2444. DOI: 10.1002/cjoc.202400262. Link
189. Fine tuning dynamic magnetism of dysprosiacarboranyl sandwiches
Yeye Liu, Qiancheng Luo, Pengbo Jin*, Yuanqi Zhai, Yanzhen Zheng*
J. Rare Earth. 2024, article accepted. DOI:10.1016/j.jre.2024.05.008. Link
188. Treatment effects of 3D-printed PCL/Fe3O4@ ZIF-8 magnetic nanocomposite on infected bone defect
Yun Xiao, Yi Ding, Jun Qiu, Xiaonan Zhang, Yanzhen Zheng, Chong Huang, Lu Zhao, Zihao Tang, Yuanli Chen, Yiwen Liu, Kezhen Zhao, Kai Guo, Li Jing, Mingchao Ding, Chunlin Zong, Jiankang He, Lei Tian
Int J Bioprint. 2024, DOI: 10.36922/ijb.2271. Link
187. Intercalating Elemental Se8 Rings and Cs+ Ions by Layered Selenidostannate: A Semiconductive Material for High-Energy Li-Ion Battery Anodes
Tengbo Wang, Hongyang Zhao, Yue-Qiao Hu,* Shujiang Ding, Zhicheng Zhang, Gao-Yang Gou, Mohamed Saber Lassoued,* and Yan-Zhen Zheng*
ACS Appl.EnergyMater. 2024, 7, 2847−285. Link
186. Bis-Alkoxide Dysprosium(III) Crown Ether Complexes Exhibit Tunable Air Stability and Record Energy Barrier
Wen-Jie Xu, Qian-Cheng Luo, Zi-Han Li, Yuan-Qi Zhai, and Yan-Zhen Zheng*
Highlight: 高性能、空气稳定的单分子磁体(SMMs)可以为信息存储器件制备提供极大的便利。而镧系SMMs的高稳定性和强磁轴向性难以平衡,因此许多高性能镝(Dy)基SMMs对空气高度敏感,这限制了它们的实际应用。具有赝D6h对称性的Dy基配合物能够很好地结合大配位数和高对称性,是制备高性能空气稳定单分子磁体的优选构型。在此,我们选择弱的18-冠-6作为平面配体,大位阻醇氧配体金刚烷醇作为轴向配体,成功合成化合物[Dy(18-C-6)(1-AdO)2][I3],其同时具有良好的空气稳定性和显著增强的磁轴向性,展现出高达2427 K的创纪录能垒值和11 K的阻塞温度,为空气稳定型SMMs设立了新的基准。
Adv. Sci. 2024, 11, 2308548. Link
185. Gd-based Molecular Coolants: Aggregating for Better Magnetocaloric Effect
Yuan-Qi Zhai, Wei-Peng Chen,* Marco Evangelisti, Zhendong Fu and Yan-Zhen Zheng*
Highlight: 作者通过溶剂热法成功合成了15种3d-Gd混金属磷酸酯配合物,其中包括7种仅含两个钆(III)离子的配合物({Gd2}、{Ni2Gd2}、{Co4Gd2}、{Co8Gd2}、{Fe6Gd2}、{Fe17Gd2})和8种含有超过两个钆(III)离子的复杂结构({Co8Gd4}、{Mn8Gd4}、{Co4Gd6}、{Mn4Gd6}、{Co6Gd8}、{Ni5Gd8}、{Ni6Gd6}、{Co8Gd8}、{Mn9Gd9})。在第一系列中,由于钆(III)二聚体周围环境的相似性,为研究磁交换作用对磁热效应(MCE)的影响提供了独特的视角。第二系列中,通过增加钆(III)中心的数量(加倍、三倍甚至四倍),作者进一步探索了在复杂环境下磁交换作用对MCE的影响。大多数配合物表现出反铁磁耦合,且MCE结果基本相似,但拓扑自旋阻挫的引入显著增强了MCE。尽管在磷酸酯配合物中观察到铁磁耦合的情况较为罕见,但本体系仍发现了一例具有出色MCE性能的配合物{Ni5Gd8},比热测试发现在1 T的低场磁熵变值达到10.7 J kg-1 K-1。此外,除了结构和拓扑的影响,作者发现磁熵变值(量度单位为焦耳/千克)与配合物中钆(III)离子所占的百分比线性相关,这为进一步理解和优化MCE提供了重要线索。
Aggregate 2024, e520. Link
184. Fine tuning Ag(I)-Sb(III) hybrid iodides for light detection
Qian-Wen Li, Mohamed Saber Lassoued, Wei-Peng Chen, Gao-Yang Gou* and Yan-Zhen Zheng*
ACS Appl. Mater. Interfaces 2024, 16, 5769–5778. Link
183. Assembly of MnIII ions into di-, tetra-, deca-nuclear coordination complexes, zero- to three-dimensional molecular frameworks: molecular spin flop to and short-range bulk magnetic spin flop ordering
Jayasree Kumar, Ibtesham Tarannum, Yan-Zhen Zheng*, Saurabh Kumar Singh* and Kartik Chandra Mondal*
CrystEngComm 2024, 26, 80-99. Link
182.Strong Antiferromagnetic Exchange-Coupling Observed in Hydride-Bridged Dimeric Dysprosium(III) Single-Molecule Magnet
Qian-Cheng Luo, Ke-Xin Yu, Peng-Bo Jin, Ye-Ye Liu, Yuan-Qi Zhai and Yan-Zhen Zheng*
Chin. J. Chem. 2024, 42, 391-396. Link
该工作被微信公众号“中国化学Chin J Chem”(LINK)报道。
181. Molar ratio induced crystal transformation from coordination complex to coordination polymers
Peng Meng#, Qian-Cheng Luo#, Aidan Brock, Xiaodong Wang, Mahboobeh Shahbazi, Aaron Micallef, John McMurtrie, Dongchen Qi, Yan-Zhen Zheng*, Jingsan Xu*
Chin. Chem. Lett. 2024, 35, 108542. Link
2023
180. Thermally Stable Terbium(II) and Dysprosium(II) Bis-amidinate Complexes
Peng-Bo Jin, Qian-Cheng Luo, Gemma K. Gransbury, Iñigo J. Vitorica-Yrezabal, Tomáš Hajdu, Ilya Strashnov, Eric J. L. McInnes, Richard E. P. Winpenny, Nicholas F. Chilton*, David P. Mills*, and Yan-Zhen Zheng*
Highlight: 作者通过增大脒基配体取代基位阻合成出脒基稀土碘化物前驱体[Ln(Piso)2I] (Ln = Tb, Dy; Piso = {(NDipp)2CtBu}, Dipp = C6H3iPr2-2,6),并分别在强还原剂石墨钾以及强亲电试剂作用下分别合成并分离出首例非常规二价稀土脒基配合物[Ln(Piso)2]及其三价同构体[Ln(Piso)2][B(C6F5)]。研究发现,大位阻脒基配体可以很好地稳定二价稀土离子,使其呈现室温稳定的中性且线性的配合物结构。通过深入研究其磁性并结合紫外可见光谱、电子顺磁共振以及理论计算等手段,确定了二价镝和二价铽离子在该配体场下表现出4fn5dz21(Ln = Tb,n = 8;Dy,n = 9)电子构型。磁性研究表明二价铽与二价镝金属中心在此配体场下产生了非常大的磁各向异性,有效磁翻转能垒分别高达1920 K和1964 K,是目前二价单核单分子磁体的新纪录。
J. Am. Chem. Soc. 2023, 145, 27993–28009. Link
该工作被微信公众号“X-MOL资讯”(LINK)和交大新闻网(LINK)报道。
179. Mitigating Raman relaxation for high-temperature single-molecule magnets
Qian-Cheng Luo and Yan-Zhen Zheng*
Highlight: 以往关于如何延长单分子磁体弛豫时间的研究主要集中在减轻磁量子隧穿效应上,但最近的研究进展表明拉曼弛豫更为关键。然而对分子体系中该弛豫机制的研究却属于是“贫瘠地带”,需要进一步被探索。本Forum文章系统梳理了单分子磁体磁弛豫过程的机制及对拉曼弛豫在分子体系的全新理解,强调了光学声子在该过程的关键作用,并通过最近几年的研究进展指出加强体系刚性和引入高能化学键对抑制拉曼过程的重要性,提出在将来结合磁光光谱技术和自旋动力学模拟等在该领域研究的必要性。总之,分子体系拉曼过程的研究是一个新兴领域,不仅对磁弛豫,而且对更广泛的物理科学具有更深的意义。
Trends Chem. 2023, 5, 869-872. Link
178. A 3D Lead Chloride Hybrid Exhibits Self-Trapped Emission and Exceptional Stability
Mohamed Saber Lassoued, Qian-Cheng Luo and Yan-Zhen Zheng*
Inorg. Chem. Front. 2023, 10, 6392-6400. Link
177.Effect of lanthanide contraction on a series of “sulfate-templated” transition-rare-earth metal clusters: Synthesis, structures and magnetic properties
Kaipeng Bai#, Pengfei Sun#, Mohamed Saber Lassoued, Caihong Fan, Chang Huang, Yanzhen Zheng, Weipeng Chen*
J. Rare Earth. 2023, article accepted. DOI:10.1016/j.jre.2023.09.005. Link
176.A Dynamic Triradical: Synthesis, Crystal Structure and Spin Frustration
Xue Dong#, Qian-Cheng Luo#, Yu Zhao, Tao Wang, Quanchun Sun, Runbo Pei, Yue Zhao, Yan-Zhen Zheng*, and Xinping Wang*
Highlight: 基于自由基的动态键化学(DCC)因在功能材料的设计合成中具有重要作用而受到广泛关注。中科院上海有机所王新平课题组与我们合作,发现了反常的自由基动态模式,即两个抗磁性化合物自组装形成三自由基。通过多种光谱实验、SQUID测试和单晶X射线衍射对三自由基进行了全面的表征。该三角形三自由基没有Jahn-Teller畸变,具有很强的自旋阻挫性质。本工作提供了一种合成多自旋有机分子新策略,而对这样一种特殊多自旋体系的研究为功能自由基在分子开关和量子材料的设计及潜在应用奠定了基础。
J. Am. Chem. Soc. 2023, 145, 17292–17298. Link
该工作被微信公众号“X-MOL资讯”(LINK)报道。
175.Electron Paramagnetic Resonance Spectra of Pentagonal Bipyramidal Gadolinium Complexes
Jonatan B. Petersen, You-Song Ding, Sandeep Gupta, Aditya Borah, Eric J. L. McInnes, Yan-Zhen Zheng, Ramaswamy Murugave and Richard E. P. Winpenny*
Inorg. Chem. 2023, 62, 8435–8441. Link
174.Synergy of Magnetic Anisotropy and Ferromagnetic Interaction Triggering a Dimeric Cr(II) Zero-Field Single-Molecule Magnet
Yuzhu Li, Zhaopeng Zeng, Yan Guo*, Xingman Liu, Yi-Quan Zhang*, Zhongwen Ouyang, Zhenxing Wang*, Xiangyu Liu*, and Yan-Zhen Zheng
Inorg. Chem. 2023, 62, 6297–6305. Link
173.Switching the Coordination Geometry to Enhance Erbium(III) Single-Molecule Magnets
Qian-Cheng Luo, Ning Ge, Yuan-Qi Zhai, Tengbo Wang, Lin Sun, Qi Sun, Fanni Li, Zhendong Fu* and Yan-Zhen Zheng*
亮点:利用一种具有大空间位阻的“硬”碱配体,成功地制备了两例铒基配合物[ErCl(OArAd)3][Na(THF)6](1)和Er(OArAd)3(2)。在不同的溶剂环境中,由于配位氯的去除,Er(III)离子周围的配位几何结构从扭曲的四面体变为扁平的三角金字塔形。这种转变显著增强了单分子磁体(SMM)的行为,使后者场致有效势垒(Ueff)达到43(1) cm−1。结合理论计算表明,强平面配体场和高局部对称性对于抑制磁量子隧穿(QTM)和实现高性能铒基SMM至关重要。
Chin. Chem. Lett. 2023, 34, 107547. LINK
172. Determinative Effect of Axial Linearity on Single-Molecule Magnet Performance in Dinuclear Dysprosium Complexes
Tian Han, You-Song Ding, Marcus J. Giansiracusa, Nicholas F. Chilton, Richard E. P. Winpenny and Yan-Zhen Zheng*
Chem. Eur. J. 2023, 29, e202300256. link
171.Tricine Supported Polyoxo(alkoxo)lanthanide Cluster {Ln15} (Ln = Eu, Gd, Tb) with Magnetic Refrigerant and Fluorescent Properties
Peng-Fei Sun, Xiao-Nan Zhang, Cai-Hong Fan, Wei-Peng Chen*, Yan-Zhen Zheng*
Polyoxometalates, 2023, 3, 9140026. Link
170. Zero-Field Splitting in Cyclic Molecular Magnet {Cr8Y8}: A High-Frequency ESR Study
Zhendong Fu, Zhong-Wen Ouyang*, Qian-Cheng Luo, Yan-Zhen Zheng*, Wei Tong, Huanpeng Bu, Hanjie Guo and Jin-Kui Zhao
Magnetochemistry 2023, 9, 49. Link
169. Two-dimensional semiconducting Cu(Ⅰ)/Sb(Ⅲ) bimetallic hybrid iodide with double perovskite structure and photocurrent response
Qian-Wen Li, Le-Yu Bi, Mohamed Saber Lassoued*, Qian-Cheng Luo, Rong Yan, Xinkai Ding, Gaoyang Gou* and Yan-Zhen Zheng*
Nanoscale, 2023, 15, 5265-5273. LInk
168.Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums
Peng Zhang,* Qian-Cheng Luo, Zhenhua Zhu, Wanrong He, Nan Song, Junting Lv, Xuning Wang, Quan-Guo Zhai,* Yan-Zhen Zheng,* Jinkui Tang*
Highlight: 报道了含有六氮杂三烯自由基(HAN·3-)和四种稀土(RE)离子的有机金属杂金属化合物[K(THF)6]{CoI[(μ3-HAN)RE2Cp*4]2} (1-RE) 和 [K(Crypt)]2{CoI[(μ3-HAN)RE2Cp*4]2} (2-RE)的合成和磁性能。1-RE显示出具有基于配体的混合价态的可分离物种,混合价态的强电子交换使2-RE中比含Gd和Dy离子的1-RE具有更强的整体铁磁行为。交流磁化率数据显示1-Dy和2-Dy都表现出缓慢的磁弛豫。重要的是,在2.0K下2-Dy的磁滞中观察到更大的矫顽力,表明与1-Dy相比,SMM行为增强。基于配体的混合价策略首次被用于改善镧系SMMs中的磁耦合,从而开辟了构建强耦合Ln SMMs的新途径。
Angew. Chem. Int. Ed. 2023, 62,e202218540. LINK
167.Slow Relaxation of Magnetization in a p-Semiquinone Radical-Bridged Dysprosium Complex
Tian Han*, Xiao-Qin Wang, Yi-Chao Chai, Yan-Zhen Zheng*
Cryst. Growth Des. 2023, 23, 24-30. Link
166. Control of pore structure by the solvent effect for efficient ethane/ethylene separation
Shao-Min Wang, Hao-Ran Liu , Su-Tao Zheng, Hao-Ling Lan, Qing-Yuan Yang*, Yan-Zhen Zheng
Sep. Purif. Technol. 2023, 304, 122378. Link
2022
165."Rationalization of Room-Temperature Single-Molecule Toroics via Exchange Coupling"
Hao-Lan Zhang, Yuan-Qi Zhai, and Yan-Zhen Zheng.
Single Molecule Toroics. Springer, Cham. 2022, pp107-131, LINK
164.Desolvation-Degree-Induced Structural Dynamics in a Rigid Cerium–Organic Framework Exhibiting Tandem Purification of Ethylene from Acetylene and Ethane
Han Fang, Bin Zheng, Zong-Hui Zhang, Peng-Bo Jin, Hong-Xin Li, Yan-Zhen Zheng, and Dong-Xu Xue*
ACS Appl. Mater. Interfaces 2022, 14, 39, 44460–44469. Link
163.Heteroleptic Dysprosium(III) Single-Molecule Magnets with Amidinate and Cyclopentadienyl Ligands
Yidian Wang, Qian-Cheng Luo, Yuan-Qi Zhai, Peng-Bo Jin, Zhendong Fu,* Qi Sun, Fan-Ni Li, and Yan-Zhen Zheng*
亮点:环戊二烯(Cp)类配体构造出目前性质最优异的镝基单分子磁体,近期研究表明环丁二烯(Cb)类配体能够提供优于Cp类配体的晶体场劈裂效应,这是一个很好的契机挖掘具有潜力的配体来构建高性能的镝基单分子磁体。本工作使用赝烯丙基型氮,氮螯合脒类配体(Am)与五甲基环戊二烯基(Cp*)进行混配给出两例Dy(III)基单分子磁体(SMMs): [AmdippDyCp*(Cl)(μ-Cl)Li(THF)3]和[{(AmiPr)-DyCp*(μ-Cl)}2]分别具有472 K和97 K的有效能垒(Ueff)。通过与构型相似的单一环戊二烯类镝基单分子磁体的对比,发现前者Ueff值与基于单一Cp*配体的Dy(III)-SMM([Cp*2DyCl2K(THF)]n)相似,同时具有更长的QTM弛豫时间7.8 s;而后者的Ueff值则是明显高于同构型的单一Cp-SMMs([(η5-Cp)2Dy(μ-Cl)]2, [(η5-Cp)2Dy(THF)(μ-Cl)]2, [(PyCp2)Dy-(μ-Cl)]2)。通过晶体结构,磁性数据和理论计算的分析,本工作提出了一种具有潜力的脒类配体,总结出该配体具有一下优势:1)更加集中的电荷分布以提供强的轴向晶体场进而增强晶体场的分裂;2)螯合配位模式和金属-配体键有助于稳定分子。
Cryst. Growth Des. 2022, 22, 6398–6404. Link
162.Reversible Thermochromism, Temperature-dependent Conductivity and High Stability for a Laminated Bismuth(III)-Silver(I) Hybrid Double Perovskite
Mohamed Saber Lassoued, Tengbo Wang, Ahmad Faizan, Qian-Wen Li, Wei-Peng Chen and Yan-Zhen Zheng*
J. Mater. Chem. C, 2022, 10, 12574-12581. Link
161.{ScnGdn} Heterometallic Rings: Tunable Ring Topology for Spin Wave Excitations
Hao-Lan Zhang, Yuan-Qi Zhai, Hiroyuki Nojiri, Christian Schröder, Hung-Kai Hsu, Yi-Tsu Chan, Zhendong Fu and Yan-Zhen Zheng*
亮点:在自旋电子和磁逻辑器件中使用自旋波的数据载体可在低功耗和无焦耳热的情况下运行,但需要小尺寸的非共线自旋结构。 由于在这种有限空间内的受控自旋波传输,异质金属环可以提供这种机会。 在这里,我们提出了一系列 {ScnGdn} (n = 4, 6, 8) 异金属环,它们是迄今为止第一个 Sc-Ln 簇,具有可调谐的自旋波激发磁相互作用。 通过时间和温度相关的自旋动力学模拟,我们能够预测 Sc4Gd4、Sc6Gd6 和 Sc8Gd8 在有限温度下的不同自旋波激发。 这种新模型以前未被开发,特别是由于反铁磁交换、偶极-偶极相互作用和低温下的环形拓扑的相互作用,体现出后者对自旋波激发的重要性。
J. Am. Chem. Soc. 2022, 144, 15193–15202. Link
该工作被微信公众号“X-MOL资讯”(LINK)和“团簇科学”(LINK)报道。
160.Suppression of zero-field quantum tunneling of magnetization by a fluorido bridge for a "very hard" 3d-4f single-molecule magnet
Bo-Kai Ling, Yuan-Qi Zhai, Peng-Bo Jin, Hong-Fan Ding, Xu-Feng Zhang, Yi Lv, Zhendong Fu, Jiewei Deng, Michael Schulze, Wolfgang Wernsdorfer and Yan-Zhen Zheng*
亮点:单分子磁体(SMM)由于阻塞温度(TB)以下的长时间弛豫而被提出用于超高密度信息存储。然而,由于磁量子隧穿(QTM)效应,许多SMMs在零场区域遭受快速磁化损失。在这里,我们表明,大的基态磁矩的产生对于抑制SMM的零场QTM至关重要。我们使用氟桥连在一例3d-4f团簇中构建镧系离子之间产生铁磁耦合。该Dy3Cr3分子具有10.7 μB的大基态磁矩,并被确认为TB为5 K的SMM。更重要的是,在0.7 K的范围内观察到了矫顽场为1.3 T、剩磁超过97%的“非常硬”的磁滞回线。从头算计算完全支持此观察结果,从而说明氟桥对于抑制基于镧系元素的SMM的零场QTM的重要性。
Matter, 2022, 5, 3485-3498. LINK
该工作被微信公众号“小柯化学”(LINK)、“DeepTech深科技”(LINK)和微博号“麻省理工科技评论”(LINK)报道。
159.Semiconductivity and High Stability in Centimetric Two-Dimensional Bismuth-Silver Hybrid Double Perovskites
Mohamed Saber Lassoued, Tengbo Wang, Qianwen Li, Xiaoyun Liu, Wei-Peng Chen, Bo Jiao, Qingyuan Yang, Zhaoxin Wu, Guijiang Zhou, Shujiang Ding, Zhicheng Zhang and Yan-Zhen Zheng*
Mater. Chem. Front., 2022, 6, 2135-2142. Link
158.Photo-Induced Phase Transition of Ce-UiO-66 into Ce-BDC-OH
Zhixiong Guo, Qian-Cheng Luo, Lei Qin, Zhimin Tian, Yan-Zhen Zheng, Yuanyuan Ma* and Yongquan Qu*
Inorg. Chem. 2022, 61, 9557-9563. LINK
157.Ligand Fluorination to Mitigate the Raman Relaxation of Dy(III) Single-Molecule Magnets: A Combined Terahertz, Far-IR and Vibronic Barrier Model Study
Yan Ma,Yuan-Qi Zhai,Qian-Cheng Luo,You-Song Ding,Yan-Zhen Zheng*
亮点:如何抑制通过虚拟能级触发的快速拉曼弛豫过程已经成为化学上设计性能更好的单分子磁体的难题。在这里,我们使用三氟甲基系统地取代原有五角双锥构型Dy基单分子磁体轴向位置叔丁醇中的甲基。所得配合物-[Dy(OLA)2py5][BPh4](LA=CH(CF3)2)− 1,CH2CF3− 2、CMe2CF3− 3) -显示逐渐增强的TBhys(@100 Oe/s),从17 K(3)、20 K(2)到23 K(1)。通过实验确定了在5–500 cm-1范围内不同的低于第一激发态能垒的弛豫能,我们确定了轴向配体的C–F键在200到350 cm−1之间的相关振动能是这一改进的关键变量。总之,这一发现不仅揭示了几何结构与拉曼过程之间的相关性,而且为如何应用振动势垒模型分析镧系单分子磁体中的多声子弛豫过程提供了范例。
Angew. Chem. Int. Ed. 2022, 61, e202206022. LINK (Hot Paper!)
该工作被微信公众号“X-MOL资讯”(LINK)和交大新闻网(LINK)报道。
156.A C,S Bonded Quasi-Two-Coordinate Chromium(II) Complex Showing Field-induced Slow Magnetic Relaxation Behaviour
Qian-Cheng Luo, Ning Ge, Yuan-Qi Zhai, Teng-Bo Wang, Lin Sun,* Qi Sun, Fanni Li, Zhongwen Ouyang, Zhen-Xing Wang* and Yan-Zhen Zheng*
亮点:尽管在过去几年中已经报道了大量由3d过渡金属离子组成的单分子磁体,但绝大多数是基于Co(II)、Fe(I、II或III),只有少数与Cr(II)离子有关,例如一些多核簇和四配位的单核配合物。此外,这些Cr(II)配合物中的配位原子主要是N和O原子。在此,我们成功地合成了一种C,S键合的单核Cr(II)化合物Cr(SAr*)2(1,HSAr*=HSC6H3-2,6(C6H2-2,4,6-Pri3)2),且在1500 Oe直流场下观察到了它的慢磁弛豫行为。利用MBO和AIM拓扑分析表明,Cr-S键可视为与格共价键,而Cr-C(ipso)相互作用更接近于离子键。通过直流磁测量、高频/场电子顺磁共振(HF-EPR)实验和从头算计算,可以确定1的相对较大的菱方特性。对模型配合物Cr(SPh)2(2)的进一步计算表明,消除分子内Cr-C(ipso)弱相互作用可以提高中心Cr(II)离子的磁轴向性。
Dalton Trans. 2022, 51, 9218-9222. LINK
155.Tetraanionic arachno-Carboranyl Ligand Imparts Strong Axiality to Terbium(III) Single-Molecule Magnets
Peng-Bo Jin, Ke-Xin Yu, Qian-Cheng Luo, Ye-Ye Liu, Yuan-Qi Zhai and Yan-Zhen Zheng*
亮点:成功地合成了一系列完全三明治结构的蛛网式碳硼烷镧系配合物,其结构为{η6-[μ-1,2-[o-C6H4(CH2)2]-1,2-C2B10H10]2Ln}{Li5(THF)10}(Ln=Tb,Dy,Ho,Er,Y),其中“碳邻接”的碳硼烷配体(arachno-C2B10H104-) 带有四个负电荷,并使用六边形η6-C2B4面与中心镧系元素离子配位。因此,中心镧系阳离子为伪十二配位,具有近似的伪D6h对称性或六角棱柱几何结构。由于这种几何结构带来的晶体场效应仍然未知,我们深入研究了这一系列配合物的磁性,发现该配体施加的晶体场导致基态和第一激发态之间的能隙为Tb>Dy>Ho>Er的关系,这与二茂铁和酞菁配体极为相似,尽管在两种配体下局部配位几何形状不同。此外,在优化磁场下,磁化反转效势垒达到445(10)K、最高可在4K观察磁滞回线,以及在2K下,钇稀释样品的弛豫时间达到193(17)秒,这一系列蛛网式碳硼烷镧系配合物的Tb类似物为Tb3+基单分子磁体提供了新的基准。
Angew. Chem. Int. Ed. 2022, 61, e202203285. LINK (Hot Paper!)
该工作被微信公众号“X-MOL资讯”(LINK)和交大新闻网(LINK)报道。
154.Comprehensive Coordination Chemistry III——3d- and 4f-Based Single Molecule Magnets
You-Song Ding, Richard E. P. Winpenny, Yan-Zhen Zheng
DOI:10.1016/B978-0-08-102688-5.00022-2. Link
153.Stable two-dimensional lead iodide hybrid materials for light detection and broadband photoluminescence
Mohamed Saber Lassoued, Yuan-Chao Pang, Qian-Wen Li, Xinkai Ding, Bo Jiao, Hua Dong, Guijiang Zhou, Shujiang Ding, Zhicheng Zhang, Zhaoxin Wu, Gaoyang Gou,* Zongyou Yin, Ju Li and Yan-Zhen Zheng*
Mater. Chem. Front., 2022, 6, 71-77. Link
152.Rigid dysprosium(III) single-molecule magnets exhibit preserved superparamagnetism in solution
Xia-Li Ding#, Qian-Cheng Luo#, Yuan-Qi Zhai, Xu-Feng Zhang, Yi Lv, Xin-Liang Zhang, Chao Ke, Chao Wu, Yan-Zhen Zheng*
亮点:具有长时间保持磁矩的分子被认为是存储字节的最小单位,这可能给信息技术带来新的革命。然而,这种分子的合理设计仍然具有挑战性。本文成功地制备了具有五角双锥配位几何结构和局部D5h对称性的具有刚性金刚烷醇配体的镝(III)配合物:[Dy(1-AdO)2(py)5]BPh4-1和[Dy(2-AdO)2(py)5]BPh4-2,因为在低能状态下振动大大减弱,它们表现出良好的单分子磁体(SMM)行为(1:Ueff≈ 1835K,TBZFC≈ 24K,TB100s≈ 17 K, TBH=23 K;2:Ueff≈ 1756K,TBZFC≈ 20K,TB100s≈ 16 K和TBH=23 K)。值得注意的是,这些固态配合物的大势垒和高的阻塞温度在溶液中得到了很好的保持,这在先前的单分子磁体的研究中从未观察到,表明使用金刚烷醇作为轴向配体可以使得配合物阳离子结构具有很强的刚性,并且足够的稳定性使固态磁性维持在了溶液中。
Chin. J. Chem. 2022, 40, 563-570. (Breaking Report) Link
该工作获得“新和成《中国化学》创新奖”(NHU-CJC Innovation Award),被微信公众号“中国化学Chin J Chem”报道,报道链接:LINK
151.Studies of the Temperature-Dependence of the Structure and Magnetism of a Hexagonal Bipyramidal Dysprosium(III) Single-Molecule Magnet
Y.-S. Ding, W. J. A. Blackmore, Y.-Q. Zhai, M. J. Giansiracusa, D. Reta, I. Vitorica-Yrezabal, R. E. P. Winpenny, N. F. Chilton* and Y.-Z. Zheng*
亮点: 利用18-冠-6为中性平面辅助配体以及轴向的阴离子型配体,成功合成出一例局部具有六方双锥构型(C6v对称性)的镝基配合物[Dy(OtBu)Cl(18-C-6)][BPh4]。该化合物具有较高的磁化反转能垒(Ueff > 1000 K),但阻塞温度却非常低(TB < 4 K)。为了搞清楚其原因,与英国曼彻斯大学的Winpenny和Chilton合作,通过变温X射线单晶衍射研究(从273K冷却到30K), 并结合从头算计算,发现该化合物结构在低温下发生了Cl-Dy-OtBu角的弯曲,从而导致电子激发态能量降低了约10%。而在低温下,通过对磁弛豫速率的温度和场依赖性的深入研究表明,该化合物的磁弛豫过程受五种不同机制的共同影响,包括了Orbach、Raman-I型、Raman-II型、QTM和声子瓶颈效应等,因此磁阻塞效应受到了极大的削弱。
Inorg. Chem., 2022, 61, 1, 227-235. Link
2021
150.A Cost-Effective Semi-Ab Initio Approach to Model Relaxation in Rare-Earth Single-Molecule Magnets
Elena Garlatti, Alessandro Chiesa, Pietro Bonfà, Emilio Macaluso, Ifeanyi J. Onuorah, Vijay S. Parmar, You-Song Ding, Yan-Zhen Zheng, Marcus J. Giansiracusa, Daniel Reta, Eva Pavarini, Tatiana Guidi, David P. Mills, Nicholas F. Chilton, Richard E. P. Winpenny, Paolo Santini, and Stefano Carretta*
亮点: 我们讨论了一种经济有效的方法来理解新一代稀土单分子磁体中的磁弛豫。它结合了晶体场参数的从头算计算、与局域模的磁弹耦合以及仅拟合三个微观参数的声子态密度的从头算计算。尽管与完全从头算方法相比要求要低得多,但该方法为观察到的弛豫的起源提供了重要的物理见解。通过将其应用于具有不同弛豫的高各向异性化合物,我们证明了该方法的可靠性,并指出了改善单分子磁体性能的思路。
J. Phys. Chem. Lett. 2021, 12, 8826−8832. LINK
149.Switching the Local Symmetry from D5h to D4h for Single-Molecule Magnets by Non-Coordinating Solvents
Xia-Li Ding, Qian-Cheng Luo, Yuan-Qi Zhai, Qian Zhang*, Lei Tian, Xinliang Zhang, Chao Ke, Xu-Feng Zhang, Yi Lv and Yan-Zhen Zheng*
亮点:观察到溶剂效应对两种单分子磁体性能的影响。四氢呋喃和甲苯溶剂可以分别在[Dy(OtBu)2(4-PhPy)5]BPh4 1和Na{[Dy(OtBu)2(4-PhPy)4][BPh4]2hf·hex 2中将赤道配位的4-苯基吡啶(4-PhPy)分子从五个切换到四个。这种交替显著改变了D5h和D4h中Dy(III)中心的局部配位对称性。磁学研究表明,2的磁各向异性能垒高于1,而由于对称效应,阻塞温度的关系正好相反。静电势的计算成功地解释了溶剂对分子结构变化的驱动力,证实了通过不同溶剂调节SMMs性能的可行性。
Inorganics 2021, 9(64). Link.
148.Methods and Models of Theoretical Calculation for Single-Molecule Magnets
Qian-Cheng Luo, Yan-Zhen Zheng*
亮点:理论计算在新兴的单分子磁体(SMMs)领域发挥着重要作用。 它不仅可以解释实验现象,还可以对合成进行指导。本综述重点讨论近年来在该领域中使用的计算方法。最常用和最有效的方法是完全活性空间自洽场方法(CASSCF),它可以很好地预测单核单分子磁体的性质。对于双核和多核单分子磁体,需要考虑磁交换,交换耦合常数可以通过蒙特卡罗模拟(MC)、通过POLY_ANISO程序的从头算计算和密度泛理论结合对称性破损态方法(DFT-BS)得到。此外还讨论了这些计算方法在设计高性能单分子磁体方面的进一步应用。
Magnetochemistry 2021, 7(8), 107. LINK
该项工作被微信公众号“MDPI化学材料”(LINK)和“科学网”(LINK)报道。
147.A Study of Cation-Dependent Inverse Hydrogen Bonds and Magnetic Exchange-Couplings in Lanthanacarborane Complexes
Peng-Bo Jin#, Qian-Cheng Luo#, Yuan-Qi Zhai, Yi-Dian Wang, Yan Ma, Lei Tian, Xin-Liang Zhang, Chao Ke, Xu-Feng Zhang, Yi Lv, Yan-Zhen Zheng*
iScience, 2021 24(7), 102760. LINK
亮点: 1. 镧系碳硼烷配合物中存在阳离子依赖的“反氢键”。2. 镧系碳硼烷二聚体通过“反氢键”的组装是可逆的。3. 这种键的平均键能大于24kJ/mol。4. 这种“反氢键”构筑出的镝基双核配合物是单分子磁体。
146. Vibronic barrier effect of magnetic relaxation in single-molecule magnets
Yuan-Qi Zhai and Yan-Zhen Zheng*
J Mater Chem C. 2021. 9, 8096-8098. Link
亮点:
单分子磁体是由磁性中心和有机配体组成的一系列配合物,而自旋和局域振动模式之间的耦合是磁弛豫的关键。由于自旋-声子耦合引起的振动势垒最近被证明为低于势垒的弛豫和异常低的拉曼指数提供了解释,这两个难题已经困扰众多研究人员了几十年,并在许多实验中普遍存在。两项研究(Phys. Rev. Lett. 2020, 125, 117203 和 Phys. Rev. B 2021, 103, 014401)阐明了它们是多光学声子辅助拉曼过程的结果,介绍了这种弛豫机制的要点和广泛含义。该理论以量子方式统一理解了不同磁弛豫过程,也适用于更一般的体系。
145.Anisotropic magnetocaloric effect in a dysprosium(III) single-molecule magnet - Commemorating the 100th anniversary of the birth of Academician Guangxian Xu
You-Song Ding and Yan-Zhen Zheng*
J. Rare Earth. 2021. 39(12), 1554-1559. Link
亮点:具有高磁各向异性的镝化合物作为单分子磁体被广泛研究。本文用单晶方法研究了Dy(III)SMM {[Dy(OSiMe3)2(4-Mepy)5(BPh4)]0.5Toluene}中的各向异性磁热效应。由于高磁各向异性,在300 K时可以观察到角变磁化。沿易轴方向测量的SMM行为与多晶样品相同。从易磁化轴到难磁化平面的旋转磁化在19 K、△B= 5T时产生的最大磁熵变为3.05kJ/kg∙K,使Dy(III)SMM可用作低温旋转磁制冷剂。
144.Hybrid Bioelastomer Reinforced by Ultrathin Nanowires of Lanthanide Hydroxycarbonates for Promising Biomedical Applications
Xinyu Zhang,Yannan Li,Juan Ge,Lei Qin,Yanzhen Zheng,Bo Lei*,Zhiping Zheng* and Yaping Du*
CCS Chem. 2021, 3, 1036–1047. Link.
143.A Giant Spin Molecule with Ninety-Six Parallel Unpaired Electrons
Lei Qin, Hao-Lan Zhang, Yuan-Qi Zhai, Hiroyuki Nojiri, Christian Schröder, Yan-Zhen Zheng*.
ISCIENCE. 2021, 24(4), 102350.Link.
This paper was rated as one of ChemRN Modelling Chemical Properties Top Ten!
142.Chelating Guanidinates for Dysprosium(III) Single-Molecule Magnets
Peng-Bo Jin, Ke-Xin Yu, Yuan-Qi Zhai, Qian-Cheng Luo, Yi-Dian Wang, Xu-Feng Zhang, Yi Lv and Yan-Zhen Zheng*
Chin. J. Chem. 2021, 39,1635-1640.Link.
141.Experimental Protection of the Spin Coherence of a Molecular Qubit Exceeding a Millisecond
Yingqiu Dai†, Yue Fu†, Zhifu Shi, Xi Qin, Shiwei Mu, Yang Wu, Ji-Hu Su, Yi-Fei Deng, Lei Qin, Yuan-Qi Zhai, Yan-Zhen Zheng, Xing Rong*,and Jiangfeng Du*
CHIN. PHYS. LETT., 2021, 38(3), 030303. Link.
140.稀土单分子磁体研究进展
李子涵,罗前程,郑彦臻*
Highlight:重稀土离子因具有大的磁矩和强的磁各向异性,在构筑高性能单分子磁体方面有着得天独厚的优势。近年来,从单核到多核,各类单分子磁体得到了迅猛的发展,涌现出了一批具有优异性质的典型代表,为本文重点综述的内容。相信随着磁-构关系的明确以及合成精准性的提升,高温单分子磁体的实现指日可待。
中国稀土学报.2021, 39(03), 391-424. Link
139.Coupling an Organic Photosensitizer and Inorganic Framework into a Single-Phase Material that Shows Visible-Light Photocurrent Response
Tao Zhang, Yue-Qiao Hu, Qian-Wen Li, Wei-Peng Chen and Yan-Zhen Zheng*
CrystEngComm, 2021, 23, 1881-1884.link
138.Magnetic Anisotropy: Structural Correlation of a Series of Chromium(II)−Amidinate Complexes
Yuan-Qi Zhai, Ning Ge, Zi-Han Li, Wei-Peng Chen, Tian Han, Zhong-Wen Ouyang, Zhenxing Wang,* and Yan-Zhen Zheng*
Inorg. Chem. 2021,60 , 3, 1344–1351, link
137.Two-dimensional semiconducting Cs(I)/Bi(III) bimetallic iodide hybrids for light detection
Mohamed Saber Lassoued,Le-Yu Bi,Zhaoxin Wu,Guijiang Zhou and Yan-Zhen Zheng*
Mater. Chem. Front., 2021,5, 973-978,link
136.Dodecanuclear {Co10Ln2} metallorings
Weipeng Chen, Tian Han, Yanzhen Zheng*
Inorganica Chimica Acta. 2021, 516, 120112. Link
135.Reentrant Spin Glass and Large Coercive Field Observed in a Spin Integer Dimerized Honeycomb Lattice
Yuan‐Qi Zhai,Yi‐Fei Deng ,Zhendong Fu*,Erxi Feng ,Yixi Su ,Takuya Shiga ,Hiroki Oshio and Yan‐Zhen Zheng*
Highlight:首例具有整数自旋值的二聚蜂窝状拓扑格子的二维范德瓦尔斯磁性材料被合成出来。该二维拓扑结构由铁及叠氮根组成,通过有机分子层间的范德华力叠加而成。该叠加最薄处只有十层,约13纳米厚。该材料兼具拓扑自旋阻挫及二维磁体的特性,表现出了新颖的再入型自旋玻璃和硬的磁体行为,矫顽场近2特斯拉。研究者坚信将二维磁体与拓扑自旋阻挫结合在一起能产生一些新奇的物理现象及材料特性,有可能开拓一个可供研究的新方向。后续工作将从减少材料的厚度、设计新的理想拓扑结构等着手开展,进一步揭示该类二维磁性材料的特性。相关结果在线发表在Advanced Functional Materials 上。
Adv. Funct. Mater.,2021, 31, 2004744,Link
134.A Local D4h Symmetric Dysprosium(III) Single‐Molecule Magnet with an Energy Barrier Exceeding 2000 K
Xia-Li Ding, Yuan-Qi Zhai,Tian Han,Wei-Peng Chen,You-Song Ding and Yan-Zhen Zheng*
Chem. Eur. J. 2021, 27, 2623-2627, link
该工作被WileyChem报道,报道链接:https://mp.weixin.qq.com/s/r2TGpK0ahC-mViFuXudW4w
133.Hendecanuclear [Cu6Gd5] magnetic cooler with high molecular symmetry of D3h
Weipeng Chen,Guojun Zhou,Zhuolun Gou, Sen Wang, Yuanqi Zhai, Tian Han, Jürgen Schnack*, Yanzhen Zheng*
Chin. Chem. Lett., 2021, 32, 838-841 link
2020
132.Highly Emissive Perylene Diimide-Based Metallacages and Their Host–Guest Chemistry for Information Encryption
Yali Hou, Zeyuan Zhang, Shuai Lu, Jun Yuan, Qiangyu Zhu, Wei-Peng Chen, Sanliang Ling, Xiaopeng Li, Yan-Zhen Zheng, Kelong Zhu, and Mingming Zhang*
J. Am. Chem. Soc. 2020, 142, 44, 18763–18768.Link
131.Constructing [CoII6] hexagon-centered heterometallic {Ln6Co6} (Ln = Y, Eu and Dy) clusters with a calix[8]arene ligand
Haitao Han,You-Song Ding,Xiaofei Zhu, Tian Han, Yan-Zhen Zheng* and Wuping Liao*
Inorg. Chem. Front.,2020, 7, 4070-4076.Link
130.Breaking the Axiality of Pentagonal-Bipyramidal Dysprosium(III) Single-Molecule Magnets with Pyrazolate Ligands
Zi-Han Li,Yuan-Qi Zhai,Wei-Peng Chen,Qian-Cheng Luo, Yan-Zhen Zheng*
Inorg. Chem. Front.,2020, 7, 4367-4376,Link
129.Large rotational magnetocaloric effect in GdVO4 single crystal
M.Y.Ruan*,Y.H.Li,L.Wang,Z.W.Ouyang,H.S.Chen,Y.Z.Zheng
Solid State Communications.2020, 320, 114018.Link
128.Terbium-fluorido cluster: an energy cage for photoluminescence
Bo-Kai Ling,Junhao Li,Yuan-Qi Zhai,Hung-Kai Hsu,Yi-Tsu Chan,WeiPeng Chen,Tian Han and Yan-Zhen Zheng*
Chem. Comm.,2020, 56, 9130-9133,Link
127. Enhancing Magnetic Hysteresis in Single-Molecule Magnets by Ligand Functionalization
Ke-Xin Yu, Jon G.C. Kragskow,You-Song Ding, Yuan-Qi Zhai, Daniel Reta, Nicholas F. Chilton*, Yan-Zhen Zheng*
Chem, 2020, 6, 1777-1793, link
Highlights:本文通过在轴向上采用带有苯基的醇氧基配体,成功地引入分子内的C−H∙∙∙π作用和分子间的C−H∙∙∙π和π∙∙∙π相互作用,增强了分子的刚性,并有效地抑制了零场量子隧穿,合成出目前最硬的D5h单离子磁体。自旋动力学计算发现,轴向配体的化学修饰改变了奥巴赫弛豫过程的起始跃迁,进而改变了与跃迁共振的振动模式。由此可见,无论是磁偶极相互作用还是超精细耦合作用,都很可能不是导致零场量子隧穿的唯一原因。分子的转振动可能扮演着不可忽略的角色。
该工作被"CellPress细胞科学"报道,报道链接:
126.A stable dysprosium(iii) complex with a terminal fluoride ligand showing high resolution luminescence and slow magnetic relaxation
Bo-Kai Ling, Yuan-Qi Zhai, Junbo Han, Tian Han* and Yan-Zhen Zheng*
Dalton Trans. 2020, 49, 6969-6973, link
Highlight:镝基单离子磁体是目前最有发展潜力的磁性储存分子材料,但现有的高性能单离子磁体很难在空气中稳定存在。在保证强的磁各向异性的同时,端基氟离子的引入可以很好地解决稳定性问题。但由于氟和稀土具有非常强的亲和力,在合成过程中很难杜绝氟离子桥连或直接与稀土生成氟化物沉淀,因此端基氟配位的镝基单离子磁体极少被报道。这里我们报道了一例具有端基氟离子配位的镝基单离子磁体:[C(NH2)3]4[DyF(piv)4](piv)2,首次利用氢键网络保护的方式,稳定端基氟离子。通过磁性和超低温荧光的分析,我们发现此例化合物具有较高的能垒,其在高配位镝基单分子磁体中名列前茅。
125.Low-temperature spin dynamics of ferromagnetic molecular ring {Cr8Y8}
Zhendong Fu*, Lei Qin, Kai Sun, Lijie Hao, Yan-Zhen Zheng, Wiebke Lohstroh, Gerrit Günther, Margarita Russina, Yuntao Liu, Yinguo Xiao, Wentao Jin & Dongfeng Chen*
npj Quant. Mater. 2020, 5, 32, link
124. Dimerized p-Semiquinone Radical Anions Stabilized by a Pair of Rare-Earth Metal Ions
Tian Han, Jonatan B. Petersen, Zi-Han Li, Yuan-Qi Zhai, Andreas Kostopoulos, Fabrizio Ortu, Eric J. L. McInnes, Richard E. P. Winpenny*, and Yan-Zhen Zheng*
Inorg. Chem.
2020, 59, 7371–7375,
link
Highlight:半醌自由基金属配合物因其独特的电子结构和氧化还原性在光电磁方面有着广泛的应用。目前文献报道研究绝大多数集中在1,2-半醌自由基金属配合物,而1,4-半醌自由基金属配合物非常少见。这里我们报道了第一例具有结构表征的1,4-半醌自由基桥连稀土配合物:{RE[(QMe4)•−Cl2(THF)3]}2 (RE = Y, Gd;QMe4•− = tetramethylquinone)。在这个双核配合物中,两个桥连的自由基采取面对面堆积形成π双聚自由基阴离子,经一系列磁学表征、电子顺磁共振和DFT计算表明分子内自由基存在很强的反铁磁耦合作用。
123. Single-Molecule Toroic Design through Magnetic Exchange Coupling
Hao-Lan Zhang, Yuan-Qi Zhai, Lei Qin, Liviu Ungur, Hiroyuki Nojiri, Yan-Zhen Zheng*
Matter, 2020, 2, 1481-1493, link
Highlights:本文报道了一例基于磁交换耦合的单分子磁环{Fe8Dy8} 1Dy。磁性测试显示,{Fe8Dy8}分子内为铁磁交换作用,在0.5 K下的M-H曲线中,在0.23特斯拉处观察到明显的S型,这是环形磁矩的主要特征。运用从头算(ab initio)方法揭示了FeIII和Dy金属中心之间的铁磁交换相互作用是产生此环形磁矩的关键。为阐明该环状分子中的Fe-Dy磁性相互作用,进一步合成了两个类似的只具有一种顺磁金属中心的化合物{Fe8Y8} 1Y和{Al8Dy8} 2Dy。比较表明,Fe-Dy的铁磁交换相互作用导致1Dy的基态与第一激发态产生了明显的能级交叉。电子顺磁共振(EPR)测试得到能级劈裂场Hc为−3.35 T,基态和第一激发态之间的能隙为107 GHz (3.55 cm−1),和从头算得出的环形磁矩与微观态一致。该单分子磁环的基态为四重简并,这在以往报道的单分子磁环(SMT)中是前所未有的。由于磁交换耦合可以为配体设计提供更多选择,因此我们的工作为下一代单分子磁环的设计提供了有效策略。
该工作被研之成理,CellPress细胞科学报道,报道链接:
122. Template Effects in Cu(I)-Bi(III) Iodide Double Perovskites: A Study of Crystal Structure, Film Orientation, Band Gap and Photocurrent Response
Le-Yu Bi, Tianli Hu, Mu-Qing Li, Bo-Kai Ling, Mohamed Saber Lassoued, Yue-Qiao Hu, Zhaoxin Wu, Guijiang Zhou and Yan-Zhen Zheng*
J. Mater. Chem. A, 2020, 8, 7288-7296, link
Highlight:铅的毒性激发了人们对制备无铅光伏材料的兴趣,其中双金属双钙钛矿(DP)策略是制备铅碘钙钛矿替代物的一种有效方法。与目前流行的Ag(I)-Bi(III)基双钙钛矿不同,在之前的工作中我们发现Cu(I)-Bi(III)基双钙钛矿具有更窄的带隙,大约1.6 eV。在这个工作中我们将展示一种使用环状脂肪胺(CAAs)的合成策略,从中我们可以看到环脂肪胺对控制Cu(I)-Bi(III)碘化物DPs的结构尺寸、薄膜取向和带隙起到至关重要的作用。在这些化合物中,使用“Z形”六元环的CAAs可以得到二维的无机结构(化合物1-5),而使用具有“C形”五元环的CAAs时得到了一维无机链(化合物6和7)。无论结构尺寸如何,这7种化合物都显示出1.53-1.67ev之间的窄带隙。我们发现当Cu-I-Bi角接近180°或八面体畸变较小时,禁带宽度较窄。此外,DFT计算表明,这种带隙具有平坦和直接的性质。有趣的是,由这些化合物形成的薄膜由于胺的对称性不同而显示出了相对于ITO基底的优先取向。对于镜面对称的二胺,无机层倾向于垂直于ITO;对于不对称二胺,无机层倾向于在ITO上随机定向;对于不对称单胺,无机层倾向于平行于ITO。这种现象在钙钛矿薄膜的制备领域还没有被报导过。为了进一步揭示这些材料在光伏应用中的潜力,我们以化合物3为代表研究了它们的光电性能。从20℃到130℃,化合物3的电导率增加了5个数量级,从3.97×10-10s/cm增加到2.78×10-5s/cm,因此化合物3表现出了标准的半导体行为。同时光电流响应实验表明这种材料在光吸收方面具有潜在的应用。
121. Piperidine Switches on Direct Band Gaps of Ag(I)/Bi(III) Bimetallic Iodide Double Perovskites
Mohamed Saber Lassoued, Le-Yu Bi, Zhaoxin Wu, Guijiang Zhou and Yan-Zhen Zheng*
J. Mater. Chem. C, 2020, 8, 5349-5354, link
Highlights:本文报道了使用银(I)和铋(III)代替铅(II)并获得两个基于二维(2D)碘化物的无铅双钙钛矿,即(AMP)4[BiAgI8]2.H2O 1和(APP)4 [ BiAg18] .H2O 2,其中AMP = 4-氨基甲基哌啶,APP = 4-氨基哌啶。与我们之前报道的基于1,4-环己二胺的化合物(C6H16N2)2 [BiAgI8] .H2O具有间接带隙相比,这两个新的2D Ag-Bi双钙钛矿由于其不易扭曲的[AgI6]单元而具有直接带隙〜2.00 eV。此外,光电流响应实验表明,两种化合物在light和dark之间的差异均超过50 nA,这表明其在光收集方面的潜在应用。1和2在热和湿气下也是稳定的。它们在95℃和90%RH下显示出高质子传导性(〜10-4 S cm-1)。因此,这项工作为设计具有直接带隙的稳定的无铅双金属碘化物双钙钛矿提供了一条新途径。
120. Understanding a Pentagonal-Bipyramidal Holmium(III) Complex with Record Energy Barrier for Magnetisation Reversal
Yan Ma, Yuan-Qi Zhai, You-Song Ding, Tian Han* and Yan-Zhen Zheng*
Chem. Commun. 2020, 56, 3979-3982, link
Highlights:本文报道了三例五角双锥构型的钬基单离子磁体,通过对轴向上配体的微调,我们发现当轴向配体为配体场较强的三甲基硅氧负离子时,合成的化合物[Ho(OSiMe3)2(py)5][BPh4]磁翻转能垒达715(6)K,是钬基单分子磁体的新纪录,理论计算结果也表明能垒的极大提升源自于微观自旋态中具有纯的基态、第一乃至第二激发态,从而自旋可以跃迁到更高的激发态来完成磁翻转,得到更大的能垒。
119. Exchange‐Biasing in a Dinuclear Dysprosium(III) Single‐Molecule Magnet with a Large Energy Barrier for Magnetization Reversal
Tian Han, Marcus J. Giansiracusa, Zi-Han Li, You-Song Ding, Nicholas F. Chilton, Richard E. P. Winpenny, and Yan-Zhen Zheng*
Chem. Eur. J. 2020, 26, 6773-6777, link
Highlights:本文采用diamine-bis(phenolate)为配体,合成了一例双氯桥连的双核镝单分子磁体,其能垒可达约1000 K,是多核单分子磁体中能垒较高的一个。该单分子磁体在高达3 K的磁滞回线中依然能够观测到磁交换-偏置效应。从头计算结果排除了单纯偶极相互作用引起的这一效应,表明氯桥连的超交换作用也起了重要的作用。
118. Rigid Amine‐Induced Pseudo‐3‐Dimensional Lead‐Free Bismuth‐Halide Perovskite with Improved Band‐Edge for Visible‐Light Absorption
Yanyan Wang, Rui Wen, Yuanyuan Liu, Le-Yu Bi, Mingming Yang, Huaming Sun, Yan-Zhen Zheng, Guofang Zhang, and Ziwei Gao*
ChemSusChem 2020, 13, 2753-2760, link
117. Dysprosiacarboranes: A New Type of Organometallic Single‐Molecule Magnet
Peng-Bo Jin, Yuan-Qi Zhai, Ke-Xin Yu, Richard E. P. Winpenny, and Yan-Zhen Zheng*
Angew. Chem. Int. Ed. 2020, 59, 9350-9354, link
Highlights:现如今,基于环戊二烯配体的夹心状金属镝配合物表现出了非常优异的单分子磁体性质,吸引了很多研究者对于这一类带离域电荷的金属有机配体的密切关注。碳硼烷是一种由碳、硼、氢三种元素组成的簇状分子,其可以与不同的碱性物质反应重组为各式各样的结构。作为一大类金属有机配体,虽然目前有很多碳硼烷金属有机配合物报道,但是其磁性方面的研究却很少。本文首次报道了镝基碳硼烷配合物单分子磁体,发现带有两个离域电荷的碳硼烷五元环平面对于金属镝能够产生很强的磁各向异性,并预测了理想的夹心状结构会产生非常优异的单分子磁体性质。我们希望这项研究能够激发更多研究者对碳硼烷稀土化学的兴趣与关注。
该工作被研之成理、交大新闻网等相继报道,报道链接:
116. The Gigantic {Ni36Gd102} Hexagon: A Sulfate-Templated “Star-of-David” for Photocatalytic CO2 Reduction and Magnetic Cooling
Wei-Peng Chen, Pei-Qin Liao, Peng-Bo Jin, Lei Zhang, Bo-Kai Ling, Shi-Cheng Wang, Yi-Tsu Chan, Xiao-Ming Chen, and Yan-Zhen Zheng*
J. Am. Chem. Soc. 2020, 142, 4663–4670, link
Highlights:本工作以JACS封面文章形式报导了一例罕见的六芒星状高核稀土-过渡金属纳米团簇——{Ni36Gd102}。该团簇具有良好的溶液稳定性,外围的金属镍离子在含氮、硫配位点的配体作用下可以选择性地在可见光催化将CO2还原为CO(90.2%),其TON为29700、转换频率为1.2 s−1,超过了多数同类型的催化剂。而该团簇含有的大量稀土钆元素则使该分子固体在2K 和ΔH = 7 T时,产生了41.3 J·kg–1·K–1的磁熵变,在低温磁制冷方面具有较好的应用潜力。该工作是我们整个稀土基纳米团簇研究课题的一个新起点,尤其是只含氮、硫配位原子的配体的引入及其无意中的原位硫酸根离子的生成对于该类材料的合成具有指导意义。而性质探索方面,此前未有报导利用团簇进行光催化还原二氧化碳分子的研究,该团簇催化下的二氧化碳还原不仅效率高、还具有很好的选择性,主要得益于具有可逆配位点的镍金属的存在,如何进一步利用该金属离子进行更有效的分子设计是留给我们的下一个课题。与此同时,如何利用团簇周围有机配体的S原子及团簇的单分散性将这类分子材料进一步器件化、并拓展其在表面磁制冷的应用也是我们需要深入思考的研究课题。目前,我们正对这些方向进行研究,希望将来能做出更多更好的工作。
该工作被科学网、研之成理、交大新闻网等报道,报道链接:
115. Equatorial coordination optimization for enhanced axiality of mononuclear Dy(iii) single-molecule magnets
Ke-Xin Yu, You-Song Ding, Yuan-Qi Zhai, Tian Han* and Yan-Zhen Zheng*
Dalton Trans. 2020, 49, 3222-3227, link
Highlights:本文合成了三个具有相似BH4-Dy-BH4轴向配位环境的镝基硼氢化合物Dy(BH4)3(THF)3 (1), [Dy(BH4)2(THF)5][BPh4] (2) and [Dy(BH4)2(18-C-6)][Na(THF)2(18-C-6)][BPh4]2 (3),三个化合物均由两个三齿的BH4–配体占据轴向配位点,但是却有不同的平面配体场。其中,化合物1的平面配位数为4,分别有三个THF和一个二齿的BH4–配位,具有变形的八面体几何构型;化合物2的平面配位数为5,有5个THF配位,具有变形的D5h局部对称性;化合物3的平面配位数为6,由18-C-6的6个O原子进行配位,具有变形的D6h局部对称性。理论计算表明,这三个化合物的磁各向异性轴都接近于BH4-Dy-BH4轴。但是,由于不同的平面配位环境,化合物1仅在加场抑制量子隧穿效应以后才能表现出慢磁驰豫行为,能垒只有37(1) K;化合物2在零场下有不明显的单分子磁体行为;而化合物3在零场下更高温度表现出单分子磁体行为,能垒约为125(21) K。由此可以发现,弱化平面配体的配位能力,有利于提升单分子磁体的性能。
114. A Study of Magnetic Relaxation in Dysprosium(III) Single‐Molecule Magnets
You-Song Ding,‡ Tian Han,‡ Yuan-Qi Zhai, Daniel Reta, Nicholas F. Chilton, Richard E. P. Winpenny,* and Yan-Zhen Zheng*
Chem. Eur. J. 2020, 26, 5893-5902, link
Highlights:围绕具有五角双锥配位环境的Dy(III)基单分子磁体,该文章展开了系统的磁构关系研究,为设计更高能垒阻塞温度的单分子磁体打下基础。该文章发现:1) 能垒与轴向配体的有效配位半径(rDy)呈线性相关, Ueff = -5032 × 2rDy + 16171 (R^2 = 0.9226),计算发现有效配位半径与配体配位原子的电负性密切相关;2)结构相似的Dy(III)基单分子磁体,呈现相似的拉曼驰豫过程,因而能垒与阻塞温度及磁滞回线开口温度也有线性关联。
2019
113. Air-Stable Hexagonal Bipyramidal Dysprosium(III) Single-Ion Magnets with Nearly Perfect D6h Local Symmetry
Zi-Han Li, Yuan-Qi Zhai, Wei-Peng Chen, You-Song Ding, and Yan-Zhen Zheng*
Chem. Eur. J. 2019, 25,16219 –16224, link
该工作被Wiley Advanced Science News报道,报道链接:
Advanced Science News:具有近乎完美D6h局部对称性的空气稳定的六角双锥镝(Ⅲ)基单离子磁体
112. Proton Transportation Behavior in Lanthanide Tartrate Metal-Organic Frameworks
Melissa Fairley, Lei Qin, Yan‐Zhen Zheng, Zhiping Zheng*
Eur. J. Inorg. Chem. 2019, 3424-3429, link
111. Two-dimensional lead-free iodide-based hybrid double perovskites: crystal growth, thin-film preparation and photocurrent responses
Le-Yu Bi, Yue-Qiao Hu, Mu-Qing Li, Tianli Hu, Hao-Lan Zhang, Xingtian Yin, Wenxiu Que, Mohamed Saber Lassoued, Yan-Zhen Zheng*
J. Mater. Chem. A, 2019, 7, 19662-19667, link
110. Imido Ligand Significantly Enhances The Effective Energy Barrier of Dysprosium(III) Single-Molecule Magnets
Bing-Cheng Liu, Ning Ge, Yuan-Qi Zhai, Tao Zhang, You-Song Ding and Yan-Zhen Zheng*
Chem. Commun., 2019, 55, 9355-9358, link
109. Dichlorido-bridged dinuclear Dy(III) single-molecule magnet with an effective energy barrier larger than 600 K
Tian Han, Yousong Ding, Zi-Han Li, Ke-Xin Yu, Yuan-Qi Zhai, Nicholas F. Chilton* and Yan-Zhen Zheng*
Chem. Commun., 2019, 55, 7930-7933, link
108. An anionic manganese(II) metal–organic framework for uranyl adsorption
Tao Zhang, Bo-Kai Ling, Yue-Qiao Hu, Tian Han and Yan-Zhen Zheng*
CrystEngComm, 2019, 21, 3901-3905, link
107. Studies of Hysteresis and Quantum Tunnelling of the Magnetisation in Dysprosium(III) Single Molecule Magnets
Fabrizio Ortu, Daniel Reta, You-Song Ding, Conrad A. P. Goodwin, Matthew P. Gregson, Eric J. L. McInnes, Richard E. P. Winpenny, Yan-Zhen Zheng*, Stephen T. Liddle*, David P. Mills*, and Nicholas F. Chilton*
Dalton Trans. 2019, 48, 8541-8545, link
106. Correlating Magnetic Anisotropy to the Subtle Coordination Geometry Variation of a Series of Cobalt(II)-Sulfonamide Complexes
Tao Wu, Yuan-Qi Zhai, Yifei Deng, Wei-Peng Chen, Tao Zhang and Yan-Zhen Zheng*
Dalton Trans. 2019, 48, 15419-15426, link
105. Two-Dimensional Silver(I)-Dithiocarboxylate Coordination Polymer Exhibiting Strong Near-Infrared Photothermal Effect
Mu-Qing Li, Min Zhao, Le-Yu Bi, Yue-Qiao Hu, Gaoyang Gou*, Ju Li*, and Yan-Zhen Zheng*
Inorg. Chem. 2019, 58, 10, 6601-6608, link
104. Air stable high-spin blatter diradicals: non-Kekulé versus Kekulé structures
Xiaoguang Hu, Lei Zhao, Hanjiao Chen,* Yousong Ding, Yan-Zhen Zheng,* Mao-sheng Miao and Yonghao Zheng*
J. Mater. Chem. C, 2019, 7, 6559-6563, link
103. Superposition of conventional and spontaneous exchange bias in a Ni50Mn34In13Fe3 magnetic shape memory alloy
Xiaoqi Liao, Yu Wang*, Erik Wetterskog, Fei Cheng, Chunxi Hao,Muhammad Tahir Khan, Yan-Zhen Zheng, Sen Yang
J. Alloy Compd. 2019, 772, 988-993, link
2018
102.A Multifunctional Lanthanide Carbonate Cluster Based Metal−Organic Framework Exhibits High Proton Transport and Magnetic Entropy Change
Qun Tang, Yan-Li Yang, Ning Zhang, Zheng Liu, Shu-Hua Zhang, Fu-Shun Tang, Jia-Yi Hu,Yan-Zhen Zheng,* and Fu-Pei Liang*
Inorg. Chem. 2018, 57, 9020−9027, link
101.Rationalization of single-molecule magnet behavior in a threecoordinate Fe(III) complex with high-spin state (S = 5/2)
Ning Ge, Yuan-Qi Zhai, Yi-Fei Deng, You-Song Ding, Tao Wu, Zhen-Xing Wang, Zhongwen Ouyang, Hiroyuki Nojiri and Yan-Zhen Zheng* ,
Inorg. Chem. Front., 2018, 5, 2486-2492 , link
100.Field- and temperature-dependent quantum tunnelling of the magnetisation in a large barrier single-molecule magnet
You-Song Ding, Ke-Xin Yu, Daniel Reta, Fabrizio Ortu, Richard E.P. Winpenny,Yan-Zhen Zheng*, Nicholas F. Chilton* ,
Nat. Commun., 2018, 9, 3134, link
99.‘‘Merged-chelating” approach for constructing high-spin Mn aggregate: A [MnIII2 ] dimer and a 2-D honeycomb network based on
star-shaped [MnIIMnIII3 ] tetrame
Jiaquan Bai, Chao Yang, Guanghua Li, Yanfeng Bi, Xiaolei Li, Jinkui Tang, Tian Han,Yan-Zhen Zheng, Gang Wu*, Shilun Qiu,
Polyhedron, 2018, 148, 44–48, link
98.Pseudotetrahedral Cobalt(II) Complexes with PNP-Ligand Showing Uniaxial Magnetic Anisotropy
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97.Quantum Monte Carlo simulations of a giant {Ni21Gd20} cage with a S =91 spin ground state
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96.Redox-Active Cobalt(II/III) Metal−Organic Framework for Selective Oxidation of Cyclohexene
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95.Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters
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94.Quantum Monte Carlo Simulations and High-Field Magnetization Studies of Antiferromagnetic Interactions in a Giant Hetero-Spin Ring
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93.A Cobalt(II) Magnetic Metal-Organic Framework with an Effective Kagomé Lattice, Large Surface Area and High SpinCanted Ordering Temperature
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92.Topological Self-Assembly of Highly-Symmetric Lanthanide Clusters: A Magnetic Study of Exchange-Coupling “Fingerprints” in Giant Gadolinium(III)
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91.Filling the Missing Links of M3n Prototype 3d-4f and 4f Cyclic Coordination Cages: Syntheses, Structures, and MagneticProperties of the Ni10Ln5
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90. Metallacrowns as Templates for Diabolo-Like {LnCu8} Complexes with Nearly Perfect Square Antiprismatic Geometry
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89. Structure Tunable Organic-Inorganic Bismuth Halides for an Enhanced Two-Dimensional Lead-Free Light-Harvesting Material
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88. Direct Observation of Confined I-…I2…I- Interactions in a Metal-Organic Framework: Iodine Capture and Sensing
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87. On balancing the QTM and the direct relaxation processes in single-ion magnets – the importance of symmetry control
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86. Copper(I)/(II)-redox triggered efficient and green rare-earth separation using a heterometallic metal–organic framework
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85. An Ising iron(II) chain exhibits a large finite-size energy barrier and “hard” magnetic behaviour
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84. Dy(III)-Carboxylate chain containing quasi-D5h sites exhibits enhanced energy barrier for magnetization reversal
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82. The Rise of Single-Ion Magnets as Spin Qubits
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81.On Approaching the Limit of Molecular Magnetic Anisotropy:A Near-Perfect Pentagonal Bipyramidal Dysprosium(III) Single-Molecule Magnet
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80.A “Molecular Water Pipe”: A Giant Tubular Cluster {Dy72} Exhibits Fast Proton Transport and Slow Magnetic Relaxation
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79.Growth of Centimeter-sized [(CH3)2NH2][Mn(HCOO)3] Hybrid Formate Perovskite Single Crystal and Raman Evidence
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78.Ferromagnetism in polynuclear systems based on non-linear [MnII2MnIII] building blocks
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77.Sulfur-centred polyoxoniobate-based 3D organic–inorganic hybrid compound and its magnetic behavior
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76.An Alkali-Ion-Insertion Approach to Structurally Transforming Metal-Organic Frameworks
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75.Large Easy-Plane Magnetic Anisotropy in a Three-Coordinate Cobalt(II) Complex [Li(THF)4][Co(NPh2)3]
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74. Hydrophobicity-Driven Self-Assembly of an Eighteen-Membered Honeycomb Lattice with Almost Classical Spins
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73.A Mixed-Ligand Approach for a Gigantic and Hollow Heterometallic Cage {Ni64RE96} for Gas Separation and Magnetic
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72.High-performance low-temperature magnetic refrigerants made of gadolinium-hydroxy-chloride
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71.Magnetic relaxations in four-coordinate Dy(III) complexes: effects of anionic surroundings and short Dy–O bonds
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70. High Quality Ultrathin Lanthanide Selenide Nanostructures with Dual Modal Functionalities
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69.Construction of magnet-type coordination polymers using high-spin {Ni4}-citrate cubane as secondary building units
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68.Syntheses, structures and magnetic properties of a series of mono- and di- nuclear dysprosium(III)-crown-ether
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67. Sodalite-like Rare-Earth Carbonate: A Study of Structural Transformation and Diluted Magnetism
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66.Influence of the Metal Ions on the Allylic Rearrangement Reaction of 3,4,5,6-Tetrahydrophthalic Anhydride
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65. Uniaxial magnetic anisotropy of square-planar chromium(II) complexes revealed by magnetic and HF-EPR studies
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64. Low-lying magnetic excitations and magnetocaloric effect of molecular magnet K6[V15As6O42(H2O)] · 8H2O
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63. Field and dilution effects on the magnetic relaxation behaviours of a 1D dysprosium(III)-carboxylate chain built from chiral ligands
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61. Polymeric Perturbation to the Magnetic Relaxations of the C2v-Symmetric [Er(Cp)2(OBu)2]− Anion
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60. Self-assembly of linear [MnII2MnIII] units with end-on azido bridges: the construction of a ferromagnetic chain using ST = 7 high-spin trimers
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59. A bottom-up synthesis of α-Fe2O3 nanoaggregates and their composites with graphene as high performance anodes in lithium-ion batteries
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56. A symbol approach for classification of molecule-based magnetic materials exemplified by coordination polymers of metal carboxylates
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55. Study of a magnetic-cooling material Gd(OH)CO3
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49. Gadolinium(III)-Hydroxy Ladders Trapped in Succinate Frameworks with Optimized Magnetocaloric Effect
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47. Switching the anisotropy barrier of a single-ion magnet by symmetry change from quasi-D5h to quasi-Oh
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46. Relaxations in Hetero-Lanthanide Dinuclear Single-Molecule Magnets
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44. Structural evolution and magnetic properties of a series of coordination polymers featuring dinuclear secondary-building units and adamantane-dicarboxylato ligands
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42. Incorporation of Spin-5/2 Chain into 2D Network with Conformational Pure e,a-cis-Cyclohexance-1,4-Dicarboxylato Linker
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41. 3D MOFs Containing Trigonal Bipyramidal Ln5 Clusters as Nodes: LargeMagnetocaloric Effect and Slow Magnetic Relaxation Behavior
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38. Co-Ln Mixed-Metal Phosphonate Grids and Cages as Molecular Magnetic Refrigerants
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37. High-Nuclearity 3d-4f Clusters as Enhanced Magnetic Coolers and Molecular Magnets
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