一个新颖的混合配体双核镝(Ⅲ)配合物:合成、结构和磁性能研究
|
摘要
通过溶剂热方法合成了一个以4′-(对苯酚)-2, 2′:6′, 2"-三联吡啶(L1)和N, N'-双(亚水杨基)亚乙二胺(L_2)为混合配体的稀土金属配合物[Dy_2(L_1)_2(L_2)Cl_2(SCN)_4],并通过单晶和粉末X-射线衍射、元素分析、红外光谱、热重分析、直流和交流磁化率对其结构和磁学性能进行了全面地表征。该配合物结晶于三斜P1空间群,晶胞参数为a=0.90268(4) nm,b=0.90572(3) nm,c=1.91170(7) nm,α=83.092(3)o,β=82.848(3)o,g=74.189(4)o,V=1.4860(11) nm~3,Z=1。在该配合物中,中性的N, N'-双(亚水杨基)亚乙二胺配体连接相邻的Dy~Ⅲ离子形成中心对称的松散双核结构,而具有大p共轭骨架的三联吡啶分子则作为封端配体参与Dy~Ⅲ离子配位多面体的构建。更为有趣的是,源于五角双锥构型的Dy~Ⅲ离子的强各向异性,该配合物呈现出场诱导的单分子磁体行为,其磁矩翻转的有效能垒和指前因子分别为42.7 K和1.3×10~(-6) s。
A new dysprosium(Ⅲ)-based complex with mixed 4'-(4-hydroxyphenyl)-2,2':6',2''-terpyridine(L_1) and N,N'-bis(salicylidene)ethylenediamine(L_2) ligands,[Dy_2(L_1)_2(L_2)Cl_2(SCN)_4],was solvothermally synthesized,and structurally and magnetically characterized by single-crystal and powder X-ray diffractions,elemental analysis,infrared spectra,thermogravimetric curve,and variable-temperature direct-and alternating-current magnetic susceptibilities.The complex crystallizes in the triclinic P1 space group with a = 0.90268(4) nm,b = 0.90572(3) nm,c = 1.91170(7) nm,α = 83.092(3)o,β = 82.848(3)o,g = 74.189(4)o,V = 1.4860(11) nm~3,Z = 1.In the crystal structure,neutral N,N-bis(salicylidene)ethylenediamine ligand aggregates two adjacent Dy~Ⅲ ions into a centrosymmetric binuclear molecule with the large p-conjugated tripyridine acting as capping ligand to complete the coordination polyhedron of Dy~Ⅲ ion.More interestingly,resulting from the strong anisotropy of the pentagonal bipyramidal Dy~Ⅲ ion,the complex displays field-induced single-molecular magnetic behavior with the effective energy barrier and pre-exponential factor of 42.7 K and 1.3×10~(–6) s.
A new dysprosium(Ⅲ)-based complex with mixed 4'-(4-hydroxyphenyl)-2,2':6',2''-terpyridine(L_1) and N,N'-bis(salicylidene)ethylenediamine(L_2) ligands,[Dy_2(L_1)_2(L_2)Cl_2(SCN)_4],was solvothermally synthesized,and structurally and magnetically characterized by single-crystal and powder X-ray diffractions,elemental analysis,infrared spectra,thermogravimetric curve,and variable-temperature direct-and alternating-current magnetic susceptibilities.The complex crystallizes in the triclinic P1 space group with a = 0.90268(4) nm,b = 0.90572(3) nm,c = 1.91170(7) nm,α = 83.092(3)o,β = 82.848(3)o,g = 74.189(4)o,V = 1.4860(11) nm~3,Z = 1.In the crystal structure,neutral N,N-bis(salicylidene)ethylenediamine ligand aggregates two adjacent Dy~Ⅲ ions into a centrosymmetric binuclear molecule with the large p-conjugated tripyridine acting as capping ligand to complete the coordination polyhedron of Dy~Ⅲ ion.More interestingly,resulting from the strong anisotropy of the pentagonal bipyramidal Dy~Ⅲ ion,the complex displays field-induced single-molecular magnetic behavior with the effective energy barrier and pre-exponential factor of 42.7 K and 1.3×10~(–6) s.
引文
[1]Chen Y C,Liu J L,Wernsdorfer W,et al,HyperfineInteraction-driven suppression of quantum tunneling at zero field in a holmium(III)single-ion magnet[J].Angew.Chem.Int.Ed,2017,56(18):4996-5000.
[2]Zhang K,Montigaud V,Cador O,et al.Tuning the Magnetic Interactions in DyIII4 Single-Molecule Magnets[J].Inorg.Chem.,2018,57(14):8550-8557.
[3]Leuenberger M N,Loss D.Quantum computing in molecular magnets.[J].Nature,2000,410(6830):789-793.
[4]Sessoli R.Materials science:Magnetic molecules back in the race[J].Nature,2017,548(7668):400-401.
[5]Liu J,Chen Y C,Liu J L,et al.A Stable pentagonal bipyramidal dy(iii)single-ion magnet with a record magnetization reversal barrier over 1000 K[J].J.Am.Chem.Soc.,2016,138(16):5441-5450.
[6]Wu J,Cador O,Li X L,et al.Axial ligand field in d4d coordination symmetry:magnetic relaxation of dy smms perturbed by counteranions[J].Inorg.Chem.,2017,56(18):11211-11219.
[7]Goodwin C A P,Ortu F,Reta D,et al.Molecular magnetic hysteresis at 60 kelvin in dysprosocenium[J].Nature,2017,548(7668):439-442.
[8]Layfield R,Guo F S,Day B,et al.A dysprosium metallocene single-molecule magnet functioning at the axial limit[J].Angew.Chem.Int.Ed.,2017,129(38):11445-11449.
[9]Chen Y C,Liu J L,Ungur L,et al.Symmetry-supported magnetic blocking at 20 k in pentagonal bipyramidal dy(iii)single-ion magnets[J].J.Am.Chem.Soc.,2016,138(8):2829-2837.
[10]Habib F,Lin P H,Long J,et al.The use of magnetic dilution to elucidate the slow magnetic relaxation effects of a Dy2 single-molecule magnet[J].J.Am.Chem.Soc,2011,133(23):8830-8833.
[11]Liu J L,Chen Y C,Tong M L.Symmetry strategies for high performance lanthanide-based single-molecule magnets[J].Chem.Soc.Rev.,2018,47(7):2431-2453.
[12]Rineharta J D,Long J R.Exploiting single-ion anisotropy in the design of f-element single-molecule magnets[J].Chem.Sci.,2011,2(11):2078-2085.
[13]Liu J L,Chen Y C,Zheng Y Z,et al.Switching the anisotropy barrier of a single-ion magnet by symmetry change from quasi-D5h to quasi-Oh[J].Chem.Sci.,2013,4(8):3310-3316.
[14]Ding Y S,Chilton N F,Winpenny R E,et al.On approaching the limit of molecular magnetic anisotropy:a near-perfect pentagonal bipyramidal dysprosium(III)single-molecule magnet[J].Angew.Chem.Int.Ed,2016,55(52):16071-16074.
[15]马东升,李伟,张秀梅,等.4,4'-二(2,2':6',2"-三联吡啶-4'-酚羟甲基)联苯(L1)的合成及结构表征[J].黑龙江大学自然科学学报,2009,26(4):522-526.
[16]Sheldrick G M.SADABS:program for empirical absorption correction of area detector data[M].Germany:University of G?ttingen,1996.
[17]Bruker A X S,SAINT.Software Reference Manual[M].Madison,WI,1998.
[18]Sheldrick G M.SHELXL-97:program for X-ray crystal structure refinement[M].Germany:University of G?ttingen,1997.
[19]Gao C,Yang Q,Wang B W,et al.Evaporable lanthanide single-ion magnet[J].CrystEngComm,2016,18(22):4165-4171.
[20]Ding Y S,Yu K X,Reta D,et al.Field-and temperaturedependent quantum tunnelling of the magnetisation in a large barrier single-molecule magnet[J].Nat.Commun.,2018,9:3134-3143.
[21]李术艳,沈淑君.2-烯-1,4-二酮及其衍生物的合成及晶体结构[J].井冈山大学学报:自然科学版,2017,38(2):35-39.
[22]黄良芳,张辉.电荷转移配合物[N-(4-氟-苄基)-3,5-二甲基吡啶][Ni(dmit)2]的合成及其晶体结构[J].井冈山大学学报:自然科学版,2013(4):28-32.
[23]Li Y,Shang Q,Zhang Y Q,et al.Fine tuning of the anisotropy barrier by ligand substitution observed in linear{Dy2Ni2}clusters[J].Chem.-Eur.J.,2016,22(52):18840-18849.
[24]Li Y,Zhao P,Zhang S,et al.A rare water and hydroxyl-extended one-dimensional dysprosium(III)chain and its magnetic dilution effect[J].Inorg.Chem.,2017,56(16):9594-9601.
[25]张杉,李言,刘正宇,等.一个新型的混合配体一维稀镝(Ⅲ)配合物:合成、结构和磁性能[J].天津师范大学学报:自然科学版,2018,38(3):46-50.
[2]Zhang K,Montigaud V,Cador O,et al.Tuning the Magnetic Interactions in DyIII4 Single-Molecule Magnets[J].Inorg.Chem.,2018,57(14):8550-8557.
[3]Leuenberger M N,Loss D.Quantum computing in molecular magnets.[J].Nature,2000,410(6830):789-793.
[4]Sessoli R.Materials science:Magnetic molecules back in the race[J].Nature,2017,548(7668):400-401.
[5]Liu J,Chen Y C,Liu J L,et al.A Stable pentagonal bipyramidal dy(iii)single-ion magnet with a record magnetization reversal barrier over 1000 K[J].J.Am.Chem.Soc.,2016,138(16):5441-5450.
[6]Wu J,Cador O,Li X L,et al.Axial ligand field in d4d coordination symmetry:magnetic relaxation of dy smms perturbed by counteranions[J].Inorg.Chem.,2017,56(18):11211-11219.
[7]Goodwin C A P,Ortu F,Reta D,et al.Molecular magnetic hysteresis at 60 kelvin in dysprosocenium[J].Nature,2017,548(7668):439-442.
[8]Layfield R,Guo F S,Day B,et al.A dysprosium metallocene single-molecule magnet functioning at the axial limit[J].Angew.Chem.Int.Ed.,2017,129(38):11445-11449.
[9]Chen Y C,Liu J L,Ungur L,et al.Symmetry-supported magnetic blocking at 20 k in pentagonal bipyramidal dy(iii)single-ion magnets[J].J.Am.Chem.Soc.,2016,138(8):2829-2837.
[10]Habib F,Lin P H,Long J,et al.The use of magnetic dilution to elucidate the slow magnetic relaxation effects of a Dy2 single-molecule magnet[J].J.Am.Chem.Soc,2011,133(23):8830-8833.
[11]Liu J L,Chen Y C,Tong M L.Symmetry strategies for high performance lanthanide-based single-molecule magnets[J].Chem.Soc.Rev.,2018,47(7):2431-2453.
[12]Rineharta J D,Long J R.Exploiting single-ion anisotropy in the design of f-element single-molecule magnets[J].Chem.Sci.,2011,2(11):2078-2085.
[13]Liu J L,Chen Y C,Zheng Y Z,et al.Switching the anisotropy barrier of a single-ion magnet by symmetry change from quasi-D5h to quasi-Oh[J].Chem.Sci.,2013,4(8):3310-3316.
[14]Ding Y S,Chilton N F,Winpenny R E,et al.On approaching the limit of molecular magnetic anisotropy:a near-perfect pentagonal bipyramidal dysprosium(III)single-molecule magnet[J].Angew.Chem.Int.Ed,2016,55(52):16071-16074.
[15]马东升,李伟,张秀梅,等.4,4'-二(2,2':6',2"-三联吡啶-4'-酚羟甲基)联苯(L1)的合成及结构表征[J].黑龙江大学自然科学学报,2009,26(4):522-526.
[16]Sheldrick G M.SADABS:program for empirical absorption correction of area detector data[M].Germany:University of G?ttingen,1996.
[17]Bruker A X S,SAINT.Software Reference Manual[M].Madison,WI,1998.
[18]Sheldrick G M.SHELXL-97:program for X-ray crystal structure refinement[M].Germany:University of G?ttingen,1997.
[19]Gao C,Yang Q,Wang B W,et al.Evaporable lanthanide single-ion magnet[J].CrystEngComm,2016,18(22):4165-4171.
[20]Ding Y S,Yu K X,Reta D,et al.Field-and temperaturedependent quantum tunnelling of the magnetisation in a large barrier single-molecule magnet[J].Nat.Commun.,2018,9:3134-3143.
[21]李术艳,沈淑君.2-烯-1,4-二酮及其衍生物的合成及晶体结构[J].井冈山大学学报:自然科学版,2017,38(2):35-39.
[22]黄良芳,张辉.电荷转移配合物[N-(4-氟-苄基)-3,5-二甲基吡啶][Ni(dmit)2]的合成及其晶体结构[J].井冈山大学学报:自然科学版,2013(4):28-32.
[23]Li Y,Shang Q,Zhang Y Q,et al.Fine tuning of the anisotropy barrier by ligand substitution observed in linear{Dy2Ni2}clusters[J].Chem.-Eur.J.,2016,22(52):18840-18849.
[24]Li Y,Zhao P,Zhang S,et al.A rare water and hydroxyl-extended one-dimensional dysprosium(III)chain and its magnetic dilution effect[J].Inorg.Chem.,2017,56(16):9594-9601.
[25]张杉,李言,刘正宇,等.一个新型的混合配体一维稀镝(Ⅲ)配合物:合成、结构和磁性能[J].天津师范大学学报:自然科学版,2018,38(3):46-50.