稀土配合物单分子磁体研究进展

doi:10.16085/j.issn.1000-6613.2016.09.024

摘要/Abstract

摘要： 单分子磁体在超高密度存储、自旋电子器件、量子计算机等领域具有潜在的应用。稀土离子因其存在高电子自旋基态以及很强的自旋轨道耦合和磁各向异性，被广泛应用于磁性材料的制备。近年来，稀土离子用来提高单分子磁体的自旋翻转能垒的研究备受关注，大量具有单分子磁体性能的稀土配合物被合成。本文综述了稀土配合物单分子磁体的合成、结构与磁性研究进展，着重介绍了单核、双核、三核、四核、五核及六核稀土配合物单分子磁体的结构与磁学性质。研究表明，应用元素镝构筑的稀土配合物单分子磁体性能最好，且随着配合物核数的增加，单分子磁体的特性更加明显。展望稀土配合物单分子磁体的研究，今后的研究重点是合成高核稀土配合物和提高磁各向异性能垒。

关键词: 单分子磁体, 单离子磁体, 稀土配合物, 磁性

Abstract: Single-molecule magnets (SMMs) have potential application in the areas of ultrahigh-density memory components,spintronic devices and quantum computers. Rare earth ions are widely used for preparation of magnetic materials due to their high spin ground state as well as strong spin orbit coupling and magnetic anisotropy. In recent years,the rare earth ions have been used to improve SMMs spin flip energy barrier and a lot of rare earth complexes have been also synthesized. In this paper,the synthesis and structures of Lanthanide-based SMMs are briefly reviewed with an emphasis on magnetism properties of the mono-,di-,tri-,tetra-,penpa-and hexa-nuclear Lanthanide SMMs. Studies have showed that the SMMs made from Dysprosium-based complexes are the best and of the more the complex nuclear,the stronger the characteristics of SMMs. The future research of Lanthanide-based SMMs should focus on the synthesis of high nuclear complexes and the advancement of magnetic anisotropy energy barrier.

Key words: single-molecule magnets, single-ion magnets, Lanthanide complexes, magnetic properties

中图分类号:

O641.4

董飘平, 梁福永, 邹征刚, 温和瑞. 稀土配合物单分子磁体研究进展[J]. 化工进展, 2016, 35(09): 2802-2817.

DONG Piaoping, LIANG Fuyong, ZOU Zhenggang, WEN Herui. Research progress on the single-molecule magnets of Lanthanide complexes[J]. Chemical Industry and Engineering Progree, 2016, 35(09): 2802-2817.

参考文献

[1] BALDOVI J J,CARDONA-SERRA S,CLEMENTEl-JUAN J M, et al. Rational design of single-ion magnets and spin qubits based on mononuclear lanthanoid complexes[J]. Inorg. Chem.,2012,51:12565-12574.
[2] NEDELKO N, KOMOWICZ A, JUSTYNIAK I, et al. Supramolecular control over molecular magnetic materials:γ-cyclodextrin-templated grid of cobalt (Ⅱ) single-ion magnets[J]. Inorganic Chemistry,2014,53(24):12870-12876.
[3] AROMI G,AGUILA D,GAMEZ P,et al. Design of magnetic coordination complexes for quantum computing[J]. Chemical Society Reviews,2012,41(2):537-546.
[4] SESSOLI R,GATTESCHI D,CANESCHI A,et al. Magnetic bistability in a metal-ion cluster[J]. Nature,1993,365(6442):141-143.
[5] ISHIKAWA N,SUGITA M,ISHIKAWA T,et al. Lanthanide double-decker complexes functioning as magnets at the single-molecular level[J]. Journal of the American Chemical Society, 2003,125(29):8694-8695.
[6] SINGH S K,GUPTA T,RAJARAMAN G. Magnetic anisotropy and mechanism of magnetic relaxation in Er(Ⅲ) single-ion magnets[J]. Inorg. Chem.,2014,53:10835-10845.
[7] CANESCHI A,GATTESCHI D,LALIOTI N,et al. Cobalt (Ⅱ)-nitronyl nitroxide chains as molecular magnetic nanowires[J]. Angewandte Chemie International Edition,2001,40(9):1760-1763.
[8] RUIZ E,CIRERA J,CANO J,et al. Can large magnetic anisotropy and high spin really coexist[J]. Chemical Communications,2008(1):52-54.
[9] LIU C M,ZHANG D Q,ZHU D B. Field-Induced single-ion magnets based on enantiopure chiral β-diketonate ligands[J]. Inorg. Chem., 2013,52:8933-8940.
[10] LI D P,WANG T W,LI C H,et al. Single-ion magnets based on mononuclear lanthanide complexes with chiral Schiff base ligands[Ln(FTA)₃L](Ln=Sm, Eu, Gd, Tb and Dy)[J]. Chemical Communications,2010,46(17):2929-2931.
[11] LIN S Y,WANG C,ZHAO L,et al. Chiral mononuclear lanthanide complexes and the field-induced single-ion magnet behaviour of a Dy analogue[J]. Dalton Transactions,2015,44(1):223-229.
[12] ZHU W H,ZHANG Y,GUO Z,et al. A simple route to a 1D ferromagnetic Dy-containing compound showing magnetic relaxation behaviour[J]. RSC Advances,2014,4(91):49934-49941.
[13] ZHU J,WANG C,LUAN F,et al. Local coordination geometry perturbed β-diketone dysprosium single-ion magnets[J]. Inorganic Chemistry,2014,53(17):8895-8901.
[14] SILVA M R,MARTIN-RAMOS P,COUTINHO J T,et al. Effect of the capping ligand on luminescent erbium (Ⅲ) β-diketonate single-ion magnets[J]. Dalton Transactions, 2014, 43(18):6752-6761.
[15] LIU S S,ZILLER J W,ZHANG Y Q,et al. A half-sandwich organometallic single-ion magnet with hexamethylbenzene coordinated to the Dy (Ⅲ) ion[J]. Chemical Communications,2014, 50(77):11418-11420.
[16] COSTES J P,AUCHEL M,DAHAN F,et al. Synthesis,structures, and magnetic properties of tetranuclear Cu^Ⅱ-Ln^Ⅲ complexes[J]. Inorganic Chemistry,2006,45(5):1924-1934.
[17] RAJARAMAN G,TOTTI F,BENCINIe A,et al. Density functional studies on the exchange interaction of a dinuclear Gd (Ⅲ)-Cu (Ⅱ)complex:method assessment,magnetic coupling mechanism and magneto-structural correlations[J]. Dalton Transactions,2009(17):3153-3161.
[18] SINGH S K,RAJARAMAN G. Decisive interactions that determine ferro/antiferromagnetic coupling in {3d-4f} pairs:a case study on dinuclear {V(IV)-Gd(Ⅲ)} complexes[J]. Dalton Transactions, 2013,42(10):3623-3630.
[19] YAMAGUCHI T,SUNATSUKI Y,ISHIDA H,et al. Synthesis, structures,and magnetic properties of face-sharing heterodinuclear Ni(Ⅱ)-Ln(Ⅲ)(Ln=Eu, Gd, Tb, Dy) complexes[J]. Inorganic Chemistry,2008,47(13):5736-5745.
[20] LONG J,VALLAT R,FERREIRA R A S,et al. A bifunctional luminescent single-ion magnet:towards correlation between luminescence studies and magnetic slow relaxation processes[J]. Chemical Communications,2012,48(80):9974-9976.
[21] POINTILLART F,LE GUENNIC B,GOLHEN S, et al. A redox-active luminescent ytterbium based single molecule magnet[J]. Chemical Communications,2013,49(6):615-617.
[22] RAJESHKUMAR T, SINGH S K, RAJARAMAN G. A computational perspective on magnetic coupling,magneto-structural correlations and magneto-caloric effect of a ferromagnetically coupled {Gd Ⅲ-Gd Ⅲ} pair[J]. Polyhedron, 2013, 52:1299-1305.
[23] ZHANG L,ZHANG P,ZHAO L,et al. Anions influence the relaxation dynamics of mono-μ₃-OH-capped triangular dysprosium aggregates[J]. Inorganic Chemistry,2015,54:5571-5578.
[24] NOJIRI H,CHOI K Y,KITAMURA N. Manipulation of the quantum tunneling of nanomagnets by using time-dependent high magnetic fields[J]. Journal of Magnetism and Magnetic Materials,2007,310(2):1468-1472.
[25] SHIMADA T,OKAZAWAA,KOJIMA N,et al. Ferromagnetic exchange couplings showing a chemical trend in Cu-Ln-Cu complexes (Ln=Gd,Tb,Dy,Ho,Er)[J]. Inorganic Chemistry,2011, 50(21):10555-10557.
[26] CHANDRASEKHAR V,PANDIAN B M,BOOMISHANKAR R, et al. Trinuclear heterobimetallic Ni₂Ln complexes[L₂Ni₂Ln] [ClO₄] (Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy, Ho,and Er;LH₃=(S)P[N(Me)N=CH-C₆H₃-2-OH-3-OMe]₃):from simple paramagnetic complexes to single-molecule magnet behavior[J]. Inorganic Chemistry,2008,47(11):4918-4929.
[27] LI X L,MIN F Y,WANG C,et al.[Ln^Ⅲ-Mn^Ⅱ-Ln^Ⅲ] heterometallic compounds:rare linear SMMs with divalent manganese ions[J]. Dalton Transactions,2015,44(7):3430-3438.
[28] ZHANG L,ZHANG P,ZHAO L, et al. Two locally chiral dysprosium compounds with salen-type ligands that show slow magnetic relaxation behavior[J]. European Journal of Inorganic Chemistry,2013,2013(8):1351-1357.
[29] KOO B H,LIM K S,RYU D W,et al. Synthesis,structures and magnetic characterizations of isostructural tetranuclear Ln₄ clusters (Ln=Dy,Ho,and Eu)[J]. Dalton Transactions,2013,42(19):7204-7209.
[30] LUAN F,LIU T,YAN P,et al. Single-molecule magnet of a tetranuclear dysprosium complex disturbed by a salen-type ligand and chloride counterions[J]. Inorganic Chemistry,2015,54(7):3485-3490.
[31] FENG W X,ZHANG Y,ZHANG Z, et al. Anion-induced self-assembly of luminescent and magnetic homoleptic cyclic tetranuclear Ln₄(Salen)₄ and Ln₄(Salen)₂ complexes (Ln=Nd,Yb, Er,or Gd)[J]. Inorganic Chemistry,2012,51(21):11377-11386.
[32] YAN P F,LIN P H,HABIB F,et al. Planar tetranuclear Dy (Ⅲ) single-molecule magnet and its Sm (Ⅲ),Gd (Ⅲ),and Tb (Ⅲ) analogues encapsulated by salen-type and β-diketonate ligands[J]. Inorganic Chemistry,2011,50(15):7059-7065.
[33] RANDELL N M,ANWAR M U, DROVER M W, et al. Self-assembled Ln₄^Ⅲ(Ln=Eu,Gd,Dy,Ho,Yb)[2×2] square grids:a new class of lanthanide cluster[J]. Inorganic Chemistry,2013,52(11):6731-6742.
[34] WOODRUFF D N, TUNA F, BODENSTEINER M, et al. Single-molecule magnetism in tetrametallic terbium and dysprosium thiolate cages[J]. Organometallics,2012,32(5):1224-1229.
[35] SU K,JIANG F,QIAN J,et al. Thiacalix [4] arene-supported kite-like heterometallic tetranuclear Zn^ⅡLn₃^Ⅲ(Ln=Gd,Tb,Dy,Ho) complexes[J]. Inorganic Chemistry,2013,52(7):3780-3786.
[36] COSTES J P,VENDIER L,WERNSDORFER W. Structural and magnetic studies of original tetranuclear Co^I-Ln^Ⅲ complexes (Ln^Ⅲ=Gd, Tb,Y)[J]. Dalton Transactions,2011,40(8):1700-1706.
[37] CHANDRASEKHAR V,BAG P,SPELDRICH M,et al. Synthesis, structure,and magnetic properties of a new family of tetra-nuclear {Mn₂^ⅢLn₂}(Ln=Dy,Gd,Tb,Ho) clusters with an arch-type topology:single-molecule magnetism behavior in the dysprosium and terbium analogues[J]. Inorganic Chemistry,2013,52(9):5035-5044.
[38] 马明亮,张秋禹,刘燕燕,等. 稀土纳米材料制备方法的研究进展[J]. 化工进展,2009,28(5):822-827.
[39] PENG J B,KONG X J,REN Y P,et al. Trigonal bipyramidal Dy5 cluster exhibiting slow magnetic relaxation[J]. Inorganic Chemistry, 2012,51(4):2186-2190.
[40] TIAN H Q,ZHAO L,LIN H,et al. Butterfly-haped pentanuclear dysprosium single-molecule magnets[J]. Chemistry-A European Journal,2013,19(39):13235-13241.
[41] LI H,SHI W,NIU Z,et al. Remarkable Ln₃^ⅢFe₂^Ⅲ clusters with magnetocaloric effect and slow magnetic relaxation[J]. Dalton Transactions,2015,44(2):468-471.
[42] CHANDRASEKHAR V,BAG P,KROENER W,et al. Pentanuclear heterometallic {Ni₂Ln₃(Ln=Gd, Dy, Tb, Ho) assemblies. single-molecule magnet behavior and multistep relaxation in the dysprosium derivative[J]. Inorganic Chemistry,2013,52(22) 13078-13086.
[43] BAG P,CHAKRABORTY A,ROGEZ G,et al. Pentanuclear heterometallic {Mn₂^ⅢLn₃}(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[J]. Inorganic Chemistry,2014,53(13):6524-6533.
[44] BURROW C E,BURCHELL T J,LIN P H,et al. Salen-based[Zn₂Ln₃] complexes with fluorescence and single-molecule-magnet properties[J]. Inorganic Chemistry,2009,48(17):8051-8053.
[45] DAS S,HOSSAIN S,DEY A,et al. Molecular magnets based on homometallic hexanuclear lanthanide (Ⅲ) complexes[J]. Inorganic Chemistry,2014,53(10):5020-5028.
[46] OSA S,KIDO T,MATSUMOTO N,et al. A tetranuclear 3d-4f single molecule magnet:[Cu^ⅡLTb^Ⅲ(hfac)₂]₂[J]. Journal of the American Chemical Society,2004,126(2):420-421.
[47] XIE Q W,CUI A L,TAO J,et al. Syntheses,structure,and magnetic properties of hexanuclear Mn₂^ⅢM₄^Ⅲ(M=Y, Gd, Tb, Dy) complexes[J]. Dalton Transactions,2012,41(35):10589-10595.
[48] KE H S,ZHAO L,GUO Y,et al. Syntheses,structures,and magnetic analyses of a family of heterometallic hexanuclear[Ni₄M₂] (M=Gd, Dy,Y) compounds:observation of slow magnetic relaxation in the Dy^Ⅲ derivative[J]. Inorganic Chemistry,2012,51(4):2699-2705.
[49] BENELLI C, GATTESCHI D. Magnetism of lanthanides in molecular materials with transition-metal ions and organic radicals[J]. Chemical Reviews,2002,102(6):2369-2388.
[50] XIONG G,QIN X Y,SHI P F,et al. New strategy to construct single-ion magnets:a unique Dy@Zn₆ cluster exhibiting slow magnetic relaxation[J]. Chemical Communications,2014,50(32):4255-4257.
[51] WANG H,KE H S,LIN S Y,et al. Heterometallic octanuclear RE₃^Ⅲ Ni₅^Ⅱ(RE=Dy^Ⅲ, Gd^Ⅲ and Y^Ⅲ) clusters with slow magnetic relaxation for the dysprosium derivative[J]. Dalton Transactions, 2013,42(15):5298-5303.
[52] LENG J D, LIU J L, TONG M L. Unique nanoscale {Cu₃₆^ⅡLn₂₄^Ⅲ}(Ln=Dy and Gd) metallo-rings[J]. Chemical mmunications,2012,48(43):5286-5288.
[53] ZHANG Z M,PAN L Y,LIN W Q,et al. Wheel-shaped nanoscale 3d-4f {Co₁₆^ⅡLn₂₄^Ⅲ} clusters (Ln=Dy and Gd)[J]. Chemical Communications,2013,49(73):8081-8083.