一个新颖的沙漏型九核镝(Ⅲ)簇合物:合成、结构和磁性能
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摘要
以2-羟基苯乙酮(HAP)为配体,采用常温挥发的方法合成了一个新颖的的沙漏型九核镝(Ⅲ)簇合物{[Dy9(μ3-OH)8(μ4-OH)2(AP)16]Cl},通过单晶和粉末X-线衍射、元素分析、红外光谱、热重分析、直流和交流变温磁化率分析对其结构和磁性能进行了全面表征.晶体结构测定结果表明:该簇合物结晶于三斜的Pī空间群,a=1.535 70(3)nm,b=2.262 32(4)nm,c=2.360 69(3)nm,α=84.287 5(13)°,β=73.944 8(14)°,γ=70.960 0(16)°,V=7.450 1(2)nm3,Z=2.该簇合物中10个羟基聚集9个稀土镝(Ⅲ)离子形成1个沙漏型Dy9内核结构,外围通过16个带负电荷的AP-配体进一步加固.磁性能测量结果表明,簇合物内镝(Ⅲ)离子间存在着弱的反铁磁相互作用,零场下呈现磁矩的慢弛豫行为,磁矩自旋翻转的有效能垒和指前因子分别为3.5 K和2.9×10~(-6) s.
A novel Dy_9 cluster with 2-hydroxyacetophenone(HAP) ligand,[Dy_9(μ3-OH)8(μ4-OH)2(AP)16]Cl,was syn-thesized by room-temperature evaporation method. The crystal structure,thermal stability and magnetic property of thecomplex were characterized by single-crystal and powder X-ray diffraction,elemental analysis,FT-IR spectrum,TG andvariable-temperature direct-and alternating current magnetic susceptibility. The determination of the crystal structureshowed that the cluster crystallizes in the triclinic Pī space group with a = 1.535 70(3)nm,b = 2.262 32(4)nm,c =2.360 69(3)nm,α = 84.287 5(13)°,β = 73.944 8(14)°,γ = 70.960 0(16)°,V = 7.450 1(2)nm3 and Z = 2. In thecluster,nine separate Dy(Ⅲ)ions are connected into a closed sandglass-shaped cluster by ten hydroxyl groups,which isfurther reinforced by sixteen negatively charged AP-ligands. The weak antiferromagnetic reaction occurs among Dy(Ⅲ)ions,and the cluster exhibits slow magnetic relaxation behavior. The effective energy barrier is 3.5 K,and the preexponentialfactor is 2.9×10~(-6) s.
A novel Dy_9 cluster with 2-hydroxyacetophenone(HAP) ligand,[Dy_9(μ3-OH)8(μ4-OH)2(AP)16]Cl,was syn-thesized by room-temperature evaporation method. The crystal structure,thermal stability and magnetic property of thecomplex were characterized by single-crystal and powder X-ray diffraction,elemental analysis,FT-IR spectrum,TG andvariable-temperature direct-and alternating current magnetic susceptibility. The determination of the crystal structureshowed that the cluster crystallizes in the triclinic Pī space group with a = 1.535 70(3)nm,b = 2.262 32(4)nm,c =2.360 69(3)nm,α = 84.287 5(13)°,β = 73.944 8(14)°,γ = 70.960 0(16)°,V = 7.450 1(2)nm3 and Z = 2. In thecluster,nine separate Dy(Ⅲ)ions are connected into a closed sandglass-shaped cluster by ten hydroxyl groups,which isfurther reinforced by sixteen negatively charged AP-ligands. The weak antiferromagnetic reaction occurs among Dy(Ⅲ)ions,and the cluster exhibits slow magnetic relaxation behavior. The effective energy barrier is 3.5 K,and the preexponentialfactor is 2.9×10~(-6) s.
引文
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[2] ADHIKARY A,JENA H S,KHATUA S,et al. Synthesis and charac-terization of two discrete Ln10 nanoscopic ladder type cages:Magneticstudies reveal a significant cryogenic magnetocaloric effect and slowmagnetic relaxation[J]. Chem Asian J,2014,9(4):1083-1090.
[3] COOKE M W,HANAN G S. Luminescent polynuclear assemblies[J].Chem Soc Rev,2007,36(9):1466-1476.
[4] SESSOLI R,TSAI H L,SCHAKE A R,et al. High-spin molecules:[Mn12O12(O2CR)16(H2O)4][J]. J Am Chem Soc,1993,115(5):1804-1816.
[5] DING Y S,CHILTON N F,WINPENNY R E P,et al. On approachingthe limit of molecular magnetic anisotropy:A near-perfect pentagonalbipyramidal dysprosium(Ⅲ)single-molecule magnet[J]. Angew ChemInt Ed,2016,55(52):16071-16074.
[6] LIU J,CHEN Y C,LIU J L,et al. A stable pentagonal bipyramidal Dy(Ⅲ)single-ion magnet with a record magnetization reversal barrierover 1000 K[J]. J Am Chem Soc,2016,138(16):5441-5450.
[7] MURUGESU M,ABBOUB K A,CHRISTOU G. New hexanuclear anddodecanuclear Fe(Ⅲ)clusters with carboxylate and alkoxide-basedligands from cluster aggregation reactions[J]. Polyhedron,2004,23(17):2779-2788.
[8] GAYNOR D,STARIKOVA Z A,OSTROVSKY S,et al. Synthesis andstructure of a heptanuclear nickel(Ⅱ)complex uniquely exhibitingfour distinct binding modes,two of which are novel,for a hydroxamate-ligand[J]. Chem Commun,2002(5):506-507.
[9] KESSISSOGLOU D P,KIRK M L,LAH M S,et al. Structural andmagnetic characterization of trinuclear,mixed-valence manganese ac-etates[J]. Inorg Chem,1992,31(26):5424-5432.
[10] XIE Y S,NI J,ZHENG F K,et al. Tetra-and binuclear complexes ofhydroxy-rich ligands:Supramolecular structures,stabilization of un-usual water clusters,and magnetic properties[J]. Cryst Growth Des,2009,9(1):118-126.
[11] SHELDRICK G M. SADABS:Program for Empirical Absorption Cor-rection of Area Detector Data[M]. Germany:University of G觟ttingen,1996.
[12] BRUKER A X S,SAINT. Software Reference Manual[M]. Madison,WI,1998.
[13] SHELDRICK G M. SHELXL-97:Program for X-ray Crystal StructureRefinement[M]. Germany:University of G觟ttingen,1997.
[14] SHELDRICK G M. SHELXS-97:Program for X-ray Crystal StructureSolution[M]. Germany:University of G觟ttingen,1997.
[15] LLUNELL M,CASANOVAL D,CIRERA J,et al. SHAPA,v2.1[M].University of Barcelona and the Hebrew University of Jerusalem,Barcelona and Jerusalem,2013.
[16] XU X B,ZHAO L,XU G F,et al. A diabolo-shaped Dy9 cluster:Syn-thesis,crystal structure and magnetic[J]. Dalton Trans,2011,40(24):6440-6444.
[17] ALEXANDROPOULOS D I,MUKHERJEE S,et al. A new family ofnonanuclear lanthanide clusters displaying magnetic and optical prop-erties[J]. Inorg Chem,2011,50(52):11276-11278.
[18] XU G,WANG Z M,HE Z,et al. Synthesis and structural characteri-zation of nonanuclear lanthanide complexes[J]. Inorg Chem,2002,41(25):6802-6807.
[19] LI Y,YANG E C,ZHAO X J,et al. Fine tuning of the anisotropy bar-rier by ligand substitution observed in linear{Dy2Ni2}clusters[J]. Chem-Eur J,2016,22(52):18840-18849.
[20] LIU S J,ZHAO J P,SONG W C,et al. Slow magnetic relaxation in twonew 1D/0D DyⅢcomplexes with a sterically hindered carboxylate lig-and[J]. Inorg Chem,2013,52(2):2103-2109.
[21] GUO Y N,CHEN X H,XUE S F,et al. Modulating magnetic dynam-ics of three Dy2 complexes through keto-enol tautomerism of the o-Vanillin picolinoylhydrazone ligand[J]. Inorg Chem,2011,50(19):9705-9713.
[22] LU Y B,JIANG X M,ZHU S D,et al. Anion effects on lanthanide(Ⅲ)tetrazole-1-acetate dinuclear complexes showing slow magnetic relax-ation and photofluorescent emission[J]. Inorg Chem,2016,55(8):3738-3749.