锰–稀土单分子磁体的研究进展
Research Progress in Mn-Ln Single Molecule Magnets
DOI: 10.12677/japc.2024.134080, PDF,    科研立项经费支持
作者: 唐正强, 徐嘉琦, 解梦婷, 胡翔宇, 梁皓然, 王窦尊, 郑 祺：南通大学化学化工学院，江苏 南通；王 金*：南通大学化学化工学院，江苏 南通；南通市智能与新能源材料及器件重点实验室，江苏 南通
关键词: 锰–稀土单分子磁体；结构；磁性；Mn-Ln Single Molecule Magnets； Structure； Magnetism
摘要: 自首例{Mn12Ac}单分子磁体(SMMs)报道以来，对高核含锰单分子磁体的研究引起了人们极大的兴趣，成为当前介观物理，磁学，纳米材料等学科的研究热点。Mn-Ln异金属单分子磁体，因为体系中含有两种不同属性的金属离子，其配位特性也不同，对于同一种配体还经常存在着竞争配位，反应往往比同核单分子磁体的反应要复杂，所以相对同核单分子磁体，Mn-Ln异金属单分子磁体报道的相对较少。因此，本文通过对近年来典型的锰–稀土SMMs进行综述，以期为3d-4f SMMs的发展奠定一定的基础。
Abstract: Since the first {Mn12Ac} single molecule magnet (SMMs) is reported, the study of high nuclear Mn-containing SMMs has aroused great interest, and has become a research hotspot in mesoscopic physics, magnetism, nanomaterials and other fields. Mn-Ln heterometallic monomolecular magnets, because the system contains two metal ions with different properties, exhibit different coordination characteristics. For the same ligand, there is often competitive coordination, and the reaction is often more complex than that of homonuclear monomolecular magnets. Thus, compared with homonuclear monomolecular magnets, Mn-Ln heterometallic monomolecular magnets have relatively few reports. Therefore, this paper reviews the typical Mn-Ln SMMs in recent years, in order to lay a certain foundation for the development of 3d-4f SMMs.
文章引用：唐正强, 徐嘉琦, 解梦婷, 胡翔宇, 梁皓然, 王窦尊, 郑祺, 王金. 锰–稀土单分子磁体的研究进展[J]. 物理化学进展, 2024, 13(4): 810-822. https://doi.org/10.12677/japc.2024.134080

参考文献

[1] Chen, L., Wang, J., Liu, Y., Song, Y., Chen, X., Zhang, Y., et al. (2014) Slow Magnetic Relaxation in Mononuclear Octahedral Manganese(III) Complexes with Dibenzoylmethanide Ligands. European Journal of Inorganic Chemistry, 2015, 271-278. [Google Scholar] [CrossRef] 
[2] Liddle, S.T. and van Slageren, J. (2015) Improving f-Element Single Molecule Magnets. Chemical Society Reviews, 44, 6655-6669. [Google Scholar] [CrossRef] [PubMed]
[3] Boudalis, A.K., Sanakis, Y., Clemente‐Juan, J.M., Donnadieu, B., Nastopoulos, V., Mari, A., et al. (2008) A Family of Enneanuclear Iron(II) Single‐Molecule Magnets. Chemistry—A European Journal, 14, 2514-2526. [Google Scholar] [CrossRef] [PubMed]
[4] Xiao, H.M. and Shi, L.C. (2012) The Application Research of Single-Molecule Magnets and Molecular Spin Electronics Materials. Advanced Materials Research, 485, 522-525. [Google Scholar] [CrossRef] 
[5] Chakraborty, A., Goura, J., Kalita, P., Swain, A., Rajaraman, G. and Chandrasekhar, V. (2018) Heterometallic 3d-4f Single Molecule Magnets Containing Diamagnetic Metal Ions. Dalton Transactions, 47, 8841-8864. [Google Scholar] [CrossRef] [PubMed]
[6] Rosado Piquer, L. and Sañudo, E.C. (2015) Heterometallic 3d-4f Single-Molecule Magnets. Dalton Transactions, 44, 8771-8780. [Google Scholar] [CrossRef] [PubMed]
[7] Jing, Y., Wang, J., Kong, M., Wang, G., Zhang, Y. and Song, Y. (2023) Detailed Magnetic Properties and Theoretical Calculation in Ferromagnetic Coupling DyIII-MII 3d-4f Complexes Based on a 1,4,7,10-Tetraazacyclododecane Derivative. Inorganica Chimica Acta, 546, Article 121301. [Google Scholar] [CrossRef] 
[8] Tian, H., Ungur, L., Zhao, L., Ding, S., Tang, J. and Chibotaru, L.F. (2018) Exchange Interactions Switch Tunneling: A Comparative Experimental and Theoretical Study on Relaxation Dynamics by Targeted Metal Ion Replacement. Chemistry—A European Journal, 24, 9928-9939. [Google Scholar] [CrossRef] [PubMed]
[9] Escobar, L.B.L., Guedes, G.P., Soriano, S., Cassaro, R.A.A., Marbey, J., Hill, S., et al. (2017) Synthesis, Crystal Structures, and EPR Studies of First MnIIILnIII Hetero-Binuclear Complexes. Inorganic Chemistry, 57, 326-334. [Google Scholar] [CrossRef] [PubMed]
[10] Wang, J., Lu, G., Liu, Y., Wu, S., Huang, G., Liu, J., et al. (2019) Building Block and Directional Bonding Approaches for the Synthesis of {DyMn4}n(n=2, 3) Metallacrown Assemblies. Crystal Growth & Design, 19, 1896-1902. [Google Scholar] [CrossRef] 
[11] Li, X., Min, F., Wang, C., Lin, S., Liu, Z. and Tang, J. (2015) [LnIII-MnII-LnIII] Heterometallic Compounds: Rare Linear Smms with Divalent Manganese Ions. Dalton Transactions, 44, 3430-3438. [Google Scholar] [CrossRef] [PubMed]
[12] Schmidt, S.F.M., Merkel, M.P., Kostakis, G.E., Buth, G., Anson, C.E. and Powell, A.K. (2017) SMM Behaviour and Magnetocaloric Effect in Heterometallic 3d-4f Coordination Clusters with High Azide: Metal Ratios. Dalton Transactions, 46, 15661-15665. [Google Scholar] [CrossRef] [PubMed]
[13] Ghazali, N.F., Vignesh, K.R., Phonsri, W., Murray, K.S., Junk, P.C., Deacon, G.B., et al. (2022) Efficient Synthetic Route to Heterobimetallic Trinuclear Complexes [Ln-Mn-Ln] and Their Single Molecule Magnetic Properties. Dalton Transactions, 51, 18502-18513. [Google Scholar] [CrossRef] [PubMed]
[14] Chandrasekhar, V., Bag, P., Speldrich, M., van Leusen, J. and Kögerler, P. (2013) Synthesis, Structure, and Magnetic Properties of a New Family of Tetra-Nuclear {Mn2IIILn2}(Ln=Dy, Gd, Tb, Ho) Clusters with an Arch-Type Topology: Single-Molecule Magnetism Behavior in the Dysprosium and Terbium Analogues. Inorganic Chemistry, 52, 5035-5044. [Google Scholar] [CrossRef] [PubMed]
[15] Akhtar, M.N., Lan, Y., Mereacre, V., Clérac, R., Anson, C.E. and Powell, A.K. (2009) Synthesis, Structures and Magnetic Properties of Heterometallic Tetranuclear Complexes. Polyhedron, 28, 1698-1703. [Google Scholar] [CrossRef] 
[16] Sun, L., Chen, H., Ma, C. and Chen, C. (2016) A New Family of Interdimer [MnII2 LnIII2]2 Clusters: Syntheses, Structures, and Magnetic Properties. Inorganic Chemistry Communications, 70, 132-135. [Google Scholar] [CrossRef] 
[17] Li, J., Wei, R., Pu, T., Cao, F., Yang, L., Han, Y., et al. (2017) Tuning Quantum Tunnelling of Magnetization through 3d-4f Magnetic Interactions: An Alternative Approach for Manipulating Single-Molecule Magnetism. Inorganic Chemistry Frontiers, 4, 114-122. [Google Scholar] [CrossRef] 
[18] Peng, Y., Singh, M.K., Mereacre, V., Anson, C.E., Rajaraman, G. and Powell, A.K. (2019) Mechanism of Magnetisation Relaxation in {MIII2DyIII2} (M=Cr, Mn, Fe, Al) “Butterfly” Complexes: How Important Are the Transition Metal Ions Here? Chemical Science, 10, 5528-5538. [Google Scholar] [CrossRef] [PubMed]
[19] Moreno Pineda, E., Chilton, N.F., Tuna, F., Winpenny, R.E.P. and McInnes, E.J.L. (2015) Systematic Study of a Family of Butterfly-Like {M2Ln2} Molecular Magnets (M=MgII, MnIII, CoII, NiII, and CuII; Ln=YIII, GdIII, TbIII, DyIII, HoIII, and ErIII). Inorganic Chemistry, 54, 5930-5941. [Google Scholar] [CrossRef] [PubMed]
[20] Lin, P., Tsui, E.Y., Habib, F., Murugesu, M. and Agapie, T. (2016) Effect of the Mn Oxidation State on Single-Molecule-Magnet Properties: MnIII vs MnIV in Biologically Inspired DyMn3O4 Cubanes. Inorganic Chemistry, 55, 6095-6099. [Google Scholar] [CrossRef] [PubMed]
[21] Bag, P., Chakraborty, A., Rogez, G. and Chandrasekhar, V. (2014) Pentanuclear Heterometallic {MnIII2Ln3} (Ln=Gd, Dy, Tb, Ho) Assemblies in an Open-Book Type Structural Topology: Appearance of Slow Relaxation of Magnetization in the Dy(III) and Ho(III) Analogues. Inorganic Chemistry, 53, 6524-6533. [Google Scholar] [CrossRef] [PubMed]
[22] Wang, H., Chen, Y., Hu, Z., Zhang, K., Zhang, Z., Song, Y., et al. (2020) Modulating the Structural Topologies and Magnetic Relaxation Behaviour of the Mn-Dy Compounds by Using Different Auxiliary Organic Ligands. New Journal of Chemistry, 44, 16302-16310. [Google Scholar] [CrossRef] 
[23] Hołyńska, M., Premužić, D., Jeon, I., Wernsdorfer, W., Clérac, R. and Dehnen, S. (2011) [MnIII6O3Ln2] Single‐Molecule Magnets: Increasing the Energy Barrier above 100 K. Chemistry—A European Journal, 17, 9605-9610. [Google Scholar] [CrossRef] [PubMed]
[24] Mishra, A., Wernsdorfer, W., Parsons, S., Christou, G. and Brechin, E.K. (2005) The Search for 3d-4f Single-Molecule Magnets: Synthesis, Structure and Magnetic Properties of a [MnIII2DyIII2] Cluster. Chemical Communications, 2005, 2086-2088. [Google Scholar] [CrossRef] [PubMed]
[25] Saha, A., Thompson, M., Abboud, K.A., Wernsdorfer, W. and Christou, G. (2011) Family of Double-Cubane Mn4Ln2 (Ln=Gd, Tb, Dy, Ho) and Mn4Y2 Complexes: A New Mn4Tb2 Single-Molecule Magnet. Inorganic Chemistry, 50, 10476-10485. [Google Scholar] [CrossRef] [PubMed]
[26] Akhtar, M.N., Lan, Y., AlDamen, M.A., Zheng, Y., Anson, C.E. and Powell, A.K. (2018) Effect of Ligand Substitution on the SMM Properties of Three Isostructural Families of Double-Cubane Mn4Ln2 Coordination Clusters. Dalton Transactions, 47, 3485-3495. [Google Scholar] [CrossRef] [PubMed]
[27] Shakeel, A., Bakhshi, H., Ahmed, T., Watanabe, L., Turnbull, M.M., Al-Harrasi, A., et al. (2023) Linear Mn(II)4Ln(III)2 (Ln=Gd, Dy, Tb) Heterometallic Complexes from a Ditopic Hydrazone Ligand: Slow Magnetic Relaxation in Mn4Dy2 Complex. Journal of Molecular Structure, 1275, 134630. [Google Scholar] [CrossRef] 
[28] Chen, H., Ma, C., Hu, M., Wen, H. and Chen, C. (2014) A Family of Novel Mn3Ln4 Clusters Displaying Single-Molecule Magnet Behavior. Dalton Trans., 43, 16737-16744. [Google Scholar] [CrossRef] [PubMed]
[29] Rigaux, G., Inglis, R., Morrison, S., Prescimone, A., Cadiou, C., Evangelisti, M., et al. (2011) Enhancing Ueff in Oxime-Bridged [MnIII6LnIII2] Hexagonal Prisms. Dalton Transactions, 40, 4797-4799. [Google Scholar] [CrossRef] [PubMed]
[30] Mereacre, V., Ako, A.M., Clérac, R., Wernsdorfer, W., Hewitt, I.J., Anson, C.E., et al. (2008) Heterometallic [Mn5‐Ln4] Single‐Molecule Magnets with High Anisotropy Barriers. Chemistry—A European Journal, 14, 3577-3584. [Google Scholar] [CrossRef] [PubMed]
[31] Karotsis, G., Kennedy, S., Teat, S.J., Beavers, C.M., Fowler, D.A., Morales, J.J., et al. (2010) [MnIII4LnIII4] Calix[4]Arene Clusters as Enhanced Magnetic Coolers and Molecular Magnets. Journal of the American Chemical Society, 132, 12983-12990. [Google Scholar] [CrossRef] [PubMed]
[32] Li, M., Ako, A.M., Lan, Y., Wernsdorfer, W., Buth, G., Anson, C.E., et al. (2010) New Heterometallic [MnIII4LnIII4] Wheels Incorporating Formate Ligands. Dalton Transactions, 39, 3375. [Google Scholar] [CrossRef] [PubMed]
[33] Li, M., Lan, Y., Ako, A.M., Wernsdorfer, W., Anson, C.E., Buth, G., et al. (2010) A Family of 3d-4f Octa-Nuclear [MnIII4LnIII4] Wheels (Ln=Sm, Gd, Tb, Dy, Ho, Er, and Y): Synthesis, Structure, and Magnetism. Inorganic Chemistry, 49, 11587-11594. [Google Scholar] [CrossRef] [PubMed]
[34] Ledezma-Gairaud, M., Grangel, L., Aromí, G., Fujisawa, T., Yamaguchi, A., Sumiyama, A., et al. (2014) From Serendipitous Assembly to Controlled Synthesis of 3d-4f Single-Molecule Magnets. Inorganic Chemistry, 53, 5878-5880. [Google Scholar] [CrossRef] [PubMed]
[35] Wang, H., Yang, F., Long, Q., Huang, Z., Chen, W., Pan, Z., et al. (2016) Two Unprecedented Decanuclear Heterometallic [MnII2MnIII6LnIII2] (Ln=Dy, Tb) Complexes Displaying Relaxation of Magnetization. Dalton Transactions, 45, 18221-18228. [Google Scholar] [CrossRef] [PubMed]
[36] Shiga, T., Onuki, T., Matsumoto, T., Nojiri, H., Newton, G.N., Hoshino, N., et al. (2009) Undecanuclear Mixed-Valence 3d-4f Bimetallic Clusters. Chemical Communications, 2009, 3568-3570. [Google Scholar] [CrossRef] [PubMed]
[37] Mereacre, V., Lan, Y., Wernsdorfer, W., Anson, C.E. and Powell, A.K. (2012) A Family of Dodecanuclear Mn11Ln Single-Molecule Magnets. Comptes Rendus. Chimie, 15, 639-646. [Google Scholar] [CrossRef] 
[38] Bagai, R., Wernsdorfer, W., Abboud, K.A. and Christou, G. (2018) Single-Molecule Magnetism within a Family of [LnIII2MnIII10] Complexes from 2-Hydroxymethylpyridine. Polyhedron, 142, 49-57. [Google Scholar] [CrossRef] 
[39] Hu, P., Wang, X., Jiang, C., Yu, F., Li, B., Zhuang, G., et al. (2018) Nanosized Chiral [Mn6Ln2] Clusters Modeled by Enantiomeric Schiff Base Derivatives: Synthesis, Crystal Structures, and Magnetic Properties. Inorganic Chemistry, 57, 8639-8645. [Google Scholar] [CrossRef] [PubMed]
[40] Stamatatos, T.C., Teat, S.J., Wernsdorfer, W. and Christou, G. (2008) Enhancing the Quantum Properties of Manganese-Lanthanide Single‐Molecule Magnets: Observation of Quantum Tunneling Steps in the Hysteresis Loops of a {Mn12Gd} Cluster. Angewandte Chemie International Edition, 48, 521-524. [Google Scholar] [CrossRef] [PubMed]
[41] Mereacre, V., Lan, Y., Clérac, R., Ako, A.M., Wernsdorfer, W., Buth, G., et al. (2011) Contribution of Spin and Anisotropy to Single Molecule Magnet Behavior in a Family of Bell-Shaped Mn11Ln2 Coordination Clusters. Inorganic Chemistry, 50, 12001-12009. [Google Scholar] [CrossRef] [PubMed]
[42] Mereacre, V.M., Ako, A.M., Clérac, R., Wernsdorfer, W., Filoti, G., Bartolomé, J., et al. (2007) A Bell-Shaped Mn11Gd2 Single-Molecule Magnet. Journal of the American Chemical Society, 129, 9248-9249. [Google Scholar] [CrossRef] [PubMed]
[43] Mishra, A., Wernsdorfer, W., Abboud, K.A. and Christou, G. (2004) Initial Observation of Magnetization Hysteresis and Quantum Tunneling in Mixed Manganese-Lanthanide Single-Molecule Magnets. Journal of the American Chemical Society, 126, 15648-15649. [Google Scholar] [CrossRef] [PubMed]
[44] Wang, X., Du, M., Xu, H., Long, L., Kong, X. and Zheng, L. (2021) Cocrystallization of Chiral 3d-4f Clusters {Mn10Ln6} and {Mn6Ln2}. Inorganic Chemistry, 60, 5925-5930. [Google Scholar] [CrossRef] [PubMed]
[45] Yu, S., Hu, H., Zou, H., Liu, D., Liang, Y., Liang, F., et al. (2022) Two Heterometallic Nanoclusters [DyIII4NiII8] and [DyIII10MnIII4MnII2]: Structure, Assembly Mechanism, and Magnetic Properties. Inorganic Chemistry, 61, 3655-3663. [Google Scholar] [CrossRef] [PubMed]
[46] Liu, J., Guo, F., Meng, Z., Zheng, Y., Leng, J., Tong, M., et al. (2011) Symmetry Related [DyIII6MnIII12] Cores with Different Magnetic Anisotropies. Chemical Science, 2, 1268-1272. [Google Scholar] [CrossRef] 
[47] Liu, J., Lin, W., Chen, Y., Leng, J., Guo, F. and Tong, M. (2012) Symmetry-Related [LnIII6MnIII12] Clusters toward Single-Molecule Magnets and Cryogenic Magnetic Refrigerants. Inorganic Chemistry, 52, 457-463. [Google Scholar] [CrossRef] [PubMed]
[48] Ako, A.M., Mereacre, V., Clérac, R., Wernsdorfer, W., Hewitt, I.J., Anson, C.E., et al. (2009) A [Mn18Dy] SMM Resulting from the Targeted Replacement of the Central MnIIIn the S = 83/2 [Mn19]-Aggregate with DyIII. Chemical Communications, 2009, 544-546. [Google Scholar] [CrossRef] [PubMed]
[49] Papatriantafyllopoulou, C., Wernsdorfer, W., Abboud, K.A. and Christou, G. (2010) Mn21Dy Cluster with a Record Magnetization Reversal Barrier for a Mixed 3d/4f Single-Molecule Magnet. Inorganic Chemistry, 50, 421-423. [Google Scholar] [CrossRef] [PubMed]
[50] Darii, M., Kravtsov, V.C., Krämer, K., Hauser, J., Decurtins, S., Liu, S., et al. (2019) Aggregation of a Giant Bean-Like {Mn26Dy6} Heterometallic Oxo-Hydroxo-Carboxylate Nanosized Cluster from a Hexanuclear {Mn6} Precursor. Crystal Growth & Design, 20, 33-38. [Google Scholar] [CrossRef]