Syntheses of new di-nuclear and tetra-nuclear lanthanide 9-anthracenecarboxylates:Magnetocaloric effect,slow magnetic relaxation and luminescent properties

Lanthanide complex-based materials with magnetic and luminescent properties have received a great deal of attention,owing to their importantly potential applications in diverse fields.In this work,the 9-anthracenecarboxylic acid(9-Haca)as bridging ligand was applied in combination with optically activeπ-conjugated 2,4,6-tri(2-pyridyl)-1,3,5-triazine(tptz)to construct a series of new di-nuclear and tetranuclear lanthanide 9-anthracenecarboxylates[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]·0.25H_(2)O(1),[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]·0.5AQ·CH_(3)COOH_(2)H_(2)O[Ln=Sm(2a),Eu(2b),Gd(2c),Tb(2d),Dy(2e),Tm(2f);AQ=9,10-anthracenedione]and[Ln_(4)(9-aca)_(10)(tptz)_(2)(CH3COO)2]·H_(2)O[Ln=Eu(3a),Gd(3b),Dy(3c)].1 displays a di-nuclear centrosymmetric moiety[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]built up from two complex[La(9-aca)_(2)(tptz)]groups bridged by one H_(2)O molecule and two syn-syn-μ2-η1:η1-9-aca-bridging ligands,while 2a-2f are isostructural and co mprise another di-nuclear centrosymmetric moieties[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]based on two complex[Ln(9-aca)_(2)(tptz)(H_(2)O)]groups connected by two syn-syn-μ2-η1:η1-9-aca-bridging ligands,3a-3c are isostructural and show tetra-nuclear centro symmetric moieties[Ln4(9-aca)10(tptz)2(CH3COO)2]containing three types of coordination modes of 9-aca-ligands.The present compounds offer the only examples of lanthanide 9-anthracenecarboxylates decorated by optically active tptz.Magnetic investigations of 2a,2c-2f,and 3b-3c indicate that 3c is typical of slow relaxation of the magnetization,while 2c and 3b show significant magnetocaloric effect(MCE)with the value of-ΔSm of 5.26 J/(kg·K)at 4 K and 15.65 J/(kg·K)at 2 K(ΔH=7 T),respectively.The luminescent properties were also studied and reveal that the characteristic luminescent properties of the 7r-conjugated aromatic ligands are introduced into magnetic lanthanide 9-anthracenecarboxylates,simultaneously exhibiting slow magnetic relaxation(or MCE)and luminescent properties.

Slow magnetic relaxation in a 3D dysprosium(Ⅲ)-fluoro-oxalate framework containing zig-zag [Dy-F]n chains

Dysprosium complexes based on [F-Dy] or near-linear [F-Dy-F] unit are of great concern in the field of single-molecule magnets due to their large magnetic anisotropy.Here,the crystal structure and the magnetic relaxation dynamics were reported for a three-dimensional(3 D) metal-organic framework(MOF):[DyF(C_(2)O_(4))(H_(2)O)2]n·2nH_(2)O(1),which is the unique MOF containing zig-zag [Dy-F]_(n) chains.Magnetic susceptibility characterization reveals that 1 is one of the few 3 D MOFs which show slow magnetic relaxation under zero dc field.And the effective energy barrier of 72 K for 1 is also higher than most Dy-based 3 D MOFs.The diamagnetic ion dilution study shows that the ferromagnetic exchange couplings mainly transmitted by F^(-) bridges in 1 contribute little to the energy barrier,but effectively suppress the quantum tunneling process and result in a smooth hysteresis loop with no waist-restricted step.

Two temperature-dependent 2D heterometallic Cd(Ⅱ)-Dy(Ⅲ)coordination polymers exhibiting slow magnetic relaxation and luminescence properties

Two unique two-dimensional(2D)Cd(Ⅱ)-Dy(Ⅲ)heterometallic coordination polymers,{[DyCd(HPMA)(PMA)_(2)(H_(2)O)_(4)]·2H_(2)O}_n(1)and[DyCd(PAA)(PMA)_(2)(H_(2)O)_(3)]_(n)(2,PAA^(-)=phenylacetate),were prepared successfully based on the phenylmalonic acid(H_(2)PMA).The construction of two polymers is sensitive to the reaction temperature and can be synthesized directionally at room temperature and 90℃,respectively.Complexes 1 and 2 display 2D layer structures that include dinuclear[Dy_(2)]cluster node and Dy(Ⅲ)-based 1D zigzag chain motif severally.The Dy(Ⅲ)-based units in two structures both are spaced well with the adjacent ones by the diamagnetic Cd(Ⅱ)-based moieties.The magnetic studies reveal that 1 and 2both display slow magnetic relaxation with temperature-dependent relaxation peaks producing an effective energy barrier(Δτ)of 74.5 and 32.1 K,separately.Furthermore,the solid-state photophysical properties of 1 and 2 show strong characteristic luminescent emissions of Dy(Ⅲ)ion in the visible region.

Magnetocaloric effect and slow magnetic relaxation behavior in binuclear rare earth based RE_(2)(L)_(2)(DMF)4(RE=Gd,Tb,and Dy) complexes

Three binuclear rare earth based complexes combining RE ions with semirigid tricarboxylic ligand(H_(3)L).namely,[RE_(2)(L)_(2)(DMF)_(4)][RE=Gd,Tb,and Dy;H_(3)L=5-((4-Carboxybenzyl)oxy)isophthalic acid;DMF=N,N-dimethylformamide]complexes,were fabricated success fully.The RE_(2)(L)_(2)(DMF)_(4) co mplexe s consist of two central RE ions with the same coordination environment which were connected by two tridentate bridging carboxylic groups and two syn-syn bidentate bridging carboxylic groups originating from the L^(3-)ligands to form the{RE_(2)}dimeric unit,and thus provides the basis for further constructing a dense three-dimensional(3 D)network structure.Moreover,the present RE_(2)(L)_(2)(DMF)_(4) complexes can be described by a topology diagram with the topology point symbol of{4^(2)·6}_(2){4^(4)·6^(2)·8^(7)·10^(2)}.Weak antiferromagnetic(AFM)coupling between the adjacent RE ions for all the present complexes was found according to the magnetic calculations.The observed significant cryogenic magnetocaloric effect(MCE)with the maximum magnetic entropy change-ΔS_(M)^(max) to be 26.3 J/(kg·K)withΔH=7 T in Gd_(2)(L)_(2)(DMF)_(4) complex makes it competitive for the cryogenic magnetic refrigerant.Moreover,the slow magnetic relaxation behavior at 0.2 T dc field with an obvious large U_(eff)/k=45(4)K and τ_(0)=6.5(2)×10^(-10)s was confirmed in Dy_(2)(L)_(2)(DMF)_(4)complex.This work not only provides an effective strategy for obtaining molecular materials with high MCE,but also confirms that tricarboxylate ligands are the ideal choice for constructing stable high dimensional geometric structures.

Synthesis of two lanthanide clusters Ln^(Ⅲ)_(4)(Gd_(4) and Dy_(4)) with [2×2] square grid shape:Magnetocaloric effect and slow magnetic relaxation behaviors

Two isostructural tetranuclear lanthanide clusters named [Ln_(4)(L)_(4)(CH_(3) O)_(4)]·CH_(3) OH(Ln=Gd(Ⅲ) for 1,Dy(Ⅲ) for 2,H_(2) L=N’-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide) were successfully isolated by using a polydentate Schiff based ligand and Ln(Ⅲ) nitrate salts.The structures of 1 and 2 were characterized by X-ray structural analyses,they are held by four double deprotonated ligands L2-.In them all the lanthanide ions are eight-coordinated and distributed over four vertices of a parallelogram,presenting a Ln4 cluster with a strict [2 × 2] square grid pattern.The details of magnetic analysis show that 1 displays weak anti-ferromagnetic exchange between neighboring Gd(Ⅲ) ions through carboxylate oxygen and methanol oxygen ligand atoms.Furthermore,1 exhibits significant magnetocaloric effect with the maximum entropy change-ΔSm value of 28.5 J/(kg K) for ΔH=7.0 T at 2.0 K.For compound 2,remarkable slow magnetic relaxation behaviors are observed in the presence of zero magnetic field with τ0=1.02 × 10^(-6) s and energy barrier ΔE/kB=43.24 K.

Two lanthanide(Ⅲ)-copper(Ⅱ) chains based on[Cu_2Ln_2]clusters exhibiting high stability,magnetocaloric effect and slow magnetic relaxation

Two 3d-4f heterometallic one-dimensional chains with neutral 4,4＇-bipyridine ligands as linkers and[Cu2Ln2] clusters （Ln = Gd for 1, Dy for 2） as nodes have been hydrothermally synthesized and structurally characterized. Magnetic studies indicate that complex 1 exhibits a relatively large magnetocaloric effect, with an entropy change -△Smax m= 24.8 J kg 1 K^-1, whilst, complex 2 features slow magnetic relaxation at low temperature.

Stepwise assembly of heterometallic 3d–4f chain exhibiting slow magnetic relaxation

The self-assembly of polyalcohol ligand 1,1,1-tris（hydroxymethyl）ethane with Dy（NO3）3· 6H2 O and Cr3O-Bzo-t-Bu precursor in the presence of triethylamine step-by-step generated a heterometallic 3d–4f chain. Magnetic investigation of the complex indicates typical slow relaxation of the magnetization at low temperature.

3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation

A 3D mixed-valence Co（Ⅲ）-Co（Ⅱ） compound [Co9（bta）10（Hbta）2（H2O）10]n·[22（H2O）]n （1） （H2bta=N,N-bis（1H-tetrazole-5- yl）-amine） was hydrothermally synthesized by reaction of Co（NO3）2·6H2O with H2bta·H2O. Compound 1 consists of three kinds of distorted-octahedral [CoⅡ（N4O2）] paramagnetic nodes which are separated by [CoⅢ（bta）2（Hbta）]2-/[CoⅢ（bta）3]3- dia- magnetic linkers to generate a 3D porous metal-organic framework （MOF） with alternative …Co（Ⅲ）…Co（II）… array and channels incorporating water molecules. Under an applied magnetic field of 4000 Oe, compound 1 exhibits slow relaxation of magnetization at low temperatures, giving AE/kB=30.O0 K and ι0=2.0×10^-8 s.

A Dinuclear Dysprosium-2-quinolinecarboxylate-1,10-Phenanthroline Compound:Crystal Structure and Magnetism

A dinuclear dysprosium（III） compound,[Dy2（μ2-OH）2（QLC）4（1,10-phen）2]·4H2O（1）（QLC-= 2-quinolinecarboxylate and 1,10-phen = 1,10-phenanthroline）,was synthesized and structurally and magnetically characterized.Compound 1 crystallizes in triclinic system,space group P1 with a = 10.9439（3）,b = 11.2823（3）,c = 12.2323（4） ？,α = 107.446（3）,β = 91.700（3）,γ = 91.511（2）°,V = 1439.25（8） A3,Z = 1,C（64）H（50）N8O（14）Dy2,Mr = 1480.12,Dc = 1.708 g/cm3,μ = 2.653 mm-1 and F（000） = 734.The final R = 0.0366 and w R = 0.0736 for 5816 observed reflections with I 〉 2σ（I）.Compound 1 contains the mononuclear [Dy（QLC）2（1,10-phen）] subunit formed from one 1,10-phen and two QLC-ligands chelating Dy（III） ion.Two mononuclear [Dy（QLC）2（1,10-phen）] subunits are bridged by a pair of μ2-OH groups to give a centrosymmetric dinuclear [Dy2（μ2-OH）2（QLC）4（1,10-phen）2] with each Dy（III） ion being eight-coordinated.Detailed susceptibility measurements revealed that compound 1 does not show slow magnetic relaxation under zero direct-current field but exhibits field-induced slow magnetic relaxation under 2 kOe applied field.

Synthesis,Structure and Magnetic Behavior of a Novel Series of Trinuclear Windwheel Complexes

A new family of trinuclear windwheel complexes with molecular formula [M^(II)_(3)(tpa)_(3)(μ-ttc)](ClO_(4))_(3)·n(sol) (ttc = 1,3,5-triazine-2,4,6-trithiol;tpa = tris(2-pyridylmethyl)amine;M = Mn,n = 2,sol = CH_(3)CN,1;M = Co,n = 1,sol = CH_(3)CN,2;M = Ni,n = 0,3) were synthesized and characterized.Single-crystal X-ray diffraction revealed that three metal centers in 1—3 are connected by ttc bridge,forming a regular triangular MII3 core.Each metal center is bonded by chelating S,N atoms from ttc and by N atoms from tpa.Magnetic studies showed that 1—3 displayed antiferromagnetic behavior and further gave the easy-axis anisotropy (D = −0.77 cm^(−1) for 1 and −8.13 cm^(−1) for 2) and easy-plane anisotropy (D = 5.08 cm^(−1) for 3).Moreover,2 exhibited field-induced slow magnetic relaxation behavior and their effective energy barriers were roughly evaluated Ueff = 6.9 K.

Engineering Heteronuclear Arrays from Ir^(Ⅲ)-Metalloligand and Co^(Ⅱ)Showing Coexistence of Slow Magnetization Relaxation and Photoluminescence

Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2·15H_(2)O(3)and{Co(H_(2)O)2[Ir(ppyCOO)_(2)(bpy)]_(2)}·2CH_(3)OH·3H_(2)O(4),have been synthe-sized by combining paramagnetic Co^(Ⅱ)ion with luminescent Ir^(Ⅲ)-metalloligand,[Ir(ppyCOOH)_(2)(bpy)][Ir(ppyCOO)_(2)(bpy)]·5H_(2)O(1),where ppyCOOH=3-(pyridin-2-yl)benzoic acid and bpy=2,2'-bipyridyl.Owing to the variable charged states of compound 1 at dif-ferent pH,compounds 2 and 3 are discrete ionic complexes containing hydrated Co^(2+)cations and deprotonated[Ir(ppyCOO)_(2)(bpy)]-anions as well as coexisting neutral[Ir(ppyCOO)(ppyCOOH)(bpy)](for 2)or Co(H_(2)O)_(4)[Ir(ppyCOO)_(2)(bpy)]_(2) trinuclear molecule(for 3).Whereas compound 4 consists of self-assembled two-dimensional coordination polymer with Co-metalloligand dative bonds.The hexa-coordinated Co^(Ⅱ)cores in all complexes display octahedral geometries with varying degrees of distortion.In a bias dc field,the ac susceptibilities for 2-4 reveal slow magnetic relaxation.Moreover,the solid-state phosphorescence is observed for compounds 2 and 3 due to weak supramolecular interaction between Co^(Ⅱ)ion and Ir-moiety but is severely quenched for 4,where the Co center is strongly connected to the metalloligand.To the best of our knowledge,this is the first report of Ir-Co systems showing both slow magnetization relaxation and photoluminescence.

Structures and magnetic properties of several novel lanthanide coordination polymers based on thiophene-2,5-dicarboxylic acid

Eight novel lanthanide complexes： {Ln（TDA）I.5（H20）2 },, （Ln = Pr（la）, Nd（2a）） and { Ln（TDA）（Ac）（H2O）}n （Ln = Pr（1）, Nd（2） Eu（3）, Gd（4）, Tb（5）, Dy（6）; TDA = Thiophene-2,5-dicarboxylic acid anion） have been constructed by hydrothermal reaction. Structural analyses reveal that complexes Ia and 2a belong to the space group C2/c, exhibiting three-dimensional （3D） frame- works. Complexes 1-6 with P2t/c space group were prepared in the presence of excessive ammonium acetate, giving rise to interesting 3D frameworks different from those of la and 2a. Magnetic property studies of 4-6 reveal the weak antiferromag- netic interaction exists between adjacent Gd3＋ in 4. The complex 6 displays rather rare slow magnetization relaxation behavior in 3D frameworks.

Switching the coordination geometry to enhance erbium(Ⅲ)single-molecule magnets

Two erbium(Ⅲ)complexes[ErCl(OAr^(Ad))_(3)][Na(THF)_(6)](1)and Er(OAr^(Ad))_(3)(2)are successfully prepared by using one variety of"hard"base ligand with large steric hindrance.The coordination geometry around the Er(Ⅲ)site changes from distorted tetrahedral to flat trigonal pyramid geometry in different solvent environment due to the removal of the coordinated chloride.Such an alternation significantly enhances the single-molecule magnet(SMM)behavior and makes the field-induced effective energy barrier(Ueff)arrive at 43(1)cm-1for the latter.Together with theoretical calculations,this study shows that strong equatorial ligand field and high local symmetry are critical to suppress the quantum tunneling of the magnetization(QTM)and achieve high-performance erbium(Ⅲ)based SMMs.

Simultaneous assembly of mononuclear and dinuclear dysprosium(Ⅲ) complexes behaving as single-molecule magnets in a one-pot hydrothermal synthesis

Two dysprosium(Ⅲ) complexes derived from 2,2'-bipyridine-6,6'-dicarboxylic acid(H_2bpdc),[Dy(bpdc)(Hbpdc)]-3H_2O(1) and[Dy_2(bpdc)_3(H_2O)_3]·2.125H_2O(2),were isolated from the same hydrothermal reaction container as different phases.Compound1 is a mononuclear complex with a DyN_4O_4 coordination polyhedron;whereas compound 2 is a dinuclear complex with two types of eight coordinated dy sprosium(Ⅲ) ions,showing DyN_4O_4 and DyN_2O_6 coordination polyhedra,respectively.Remarkably,a new type of(H_2O)_6 supramolecular aggregate exists in the crystal structure of 2.Magnetic investigations revealed that 1 is a field-induced single-ion magnet with an effective energy barrier of 45.6 K,exhibiting two-step magnetic relaxation;while an intramolecular ferromagnetic interaction exists in 2,which is a field-induced single-molecule magnet,displaying two-step magnetic relaxation too,with effective energy barriers of 53.4 and 92.1 K,respectively.