Novel heterometallic 3d-4f metal-azido complex of mixed ligands with unprecedented structure type: synthesis, structure, and magnetic properties

A novel heterometallic 3d-4f metal-azido complex of mixed ligands, showing unprecedented structure type and interesting magnetic properties, has been hydrothermally synthesized and characterized.     

High-nuclearity 3d-4f [FeIII5LnIII8] complexes: synthesis, structure and magnetic properties

The isostructural tridecanuclear mixed-metal [FeIII5LnIII8] (Ln = Pr, Nd, Gd) aggregates are the largest [Fe-Ln] clusters reported to date and the magnetic properties suggest a ferrimagnetic arrangement in [Fe5Pr8] and [Fe5Nd8], whereas for [Fe5Gd8] ferromagnetic interactions are dominant leading to a large spin ground state.     

First 3D 3d-4f interpenetrating structure: synthesis, reaction, and characterization of {[LnCr(IDA)2(C2O4)]}n

The hydrothermal reaction of Cr(NO3)3, Ln2O3, and iminodiacetate acid (H(2)IDA) in the molar ratio of 1:1:3 produced {[LnCr(IDA)2(C2O4)]}n (Ln = Eu, 1; Sm, 2), which represent the first 3D 3d-4f interpenetrating coordination polymers. In the reaction, the H(2)IDA ligands partly decompose into oxalate anions (ox), which connect Ln(III) ions to form 1D {Ln(ox)}n chains. Each of the Cr(III) ions is tridentate-coordinated by two IDA ligands, which act as tetradentate metalloligands to link {Ln(ox)}n chains to form 3D open networks. The two open networks interpenetrate each other to form nonporous products. 1 and 2 are thermally stable up to 327 and 360 degrees C, respectively. Both of complexes show normally paramagnetic behavior. The luminescent results imply that the energy transfers from Ln(III) to Cr(III) are strong.     

Construction of 1-D 4f and 3d-4f coordination polymers with flexible Schiff base ligands

Three new lanthanide 1-D coordination polymers ({[Ln(2)(H(2)L)(OAc)(6)]·EtOH·2H(2)O}(n) (Ln = Eu (1), Er (2)) and {YbNiLCl(OAc)(2)(H(2)O)}(n) (3)) and a heterobinuclear complex [YbNiLCl(3)(H(2)O)(3)] (4) are reported which are formed from salen type Schiff-base ligands H(2)L (H(2)L = N,N'-bis(3-methoxysalicylidene)butane-1,4-diamine). The polymeric structures are formed by bridging H(2)L units in the case of 1 and 2, and by acetate groups in 3. The structures of 1-4 were determined by single crystal X-ray crystallographic studies and their luminescence properties in MeCN solution were determined.     

Three-dimensional 3d-4f heterometallic coordination polymers: synthesis, structures, and magnetic properties

Three new 3d-4f heterometallic coordination polymers, [Ln(2)(H(2)O)(4)M(2)(H(2)O)(2)(QA)(5)].nH(2)O (H(2)QA = quinolinic acid; Ln = Gd, M = Ni, n = 7 (1); Ln = Gd, M = Co, n = 6.5 (2); Ln = Dy, M = Co, n = 6.5 (3)), have been synthesized through hydrothermal pretreatment and cooling-down crystallization. These compounds possess the isostructural 3D frameworks with 1D chairlike channels along the c axis, which are occupied by noncoordinating water molecules. Crystal data: for 1, C(35)H(41)Gd(2)Ni(2)N(5)O(33), orthorhombic, space group Pna2(1), with a = 28.567(6) A, b = 14.498(3) A, c = 12.250(2) A, and Z = 4; for 2, C(35)H(40)Gd(2)Co(2)N(5)O(32.5), orthorhombic, space group Pna2(1), with a = 28.843(3) A, b = 14.4325(13) A, c = 12.2275(9) A, and Z = 4; for 3, C(35)H(40)Dy(2)Co(2)N(5)O(32.5), orthorhombic, space group Pna2(1), with a = 28.8471(14) A, b = 14.4534(10) A, c = 12.2520(7) A, and Z = 4. The magnetic behaviors for the three compounds have been investigated.     

Construction of 3d-4f mixed-metal complexes based on a binuclear oxovanadium unit: synthesis, crystal structure, EPR, and magnetic properties

The oxovanadium(IV)-lanthanide(III) heteronuclear complexes, [[Ce(H2O)7(VO)(TTHA)0.5][(VO)2(TTHA)]].8H2O (2), [Pr(H2O)7(VO)3(TTHA)1.5].10H2O (3), and [Nd(H2O)7(VO)3(TTHA)(1.5)].10H2O (4) (H6TTHA = triethylenetetraaminehexaacetic acid), were prepared based on a binuclear building block of [(VO)2(TTHA)]2- in [VO(H2O)5][(VO)2TTHA].4H2O (1). The X-ray crystallographic studies show that 1 is an ion-pair complex, containing the [(VO)2(TTHA)]2- unit as a useful building block. Adding the light Ln3+ ions to this synthesis system, three new 3d-4f mixed-metal-based complexes were obtained. Although the light lanthanide ions always exhibit similar chemical behavior, the structures of 2-4 are not homologous. 2 is exhibited as a one-dimensional coordination polymer, comprising an unusual Ce2V2 heterometallic lattice in the chain structure, which is the second report of a oxovanadium(IV)-lanthanide(III) coordination polymer. 3 and 4 are isomorphic, every two of the Ln3+ cations linked three [(VO)2(TTHA)]2- anions, forming an interesting linear octanuclear structure. This kind of heteronuclear linear complex is rather rare, which expands the realm of 3d-4f complexes. Further investigations such as IR spectra, UV-vis spectra, magnetic properties, and EPR spectra were studied, and a detailed discussion is given for this system.     

Heptanuclear 3d-4f cluster complexes with a coaxial double-screw-propeller topology and diverse magnetic properties

Two novel coaxial double-screw-propeller heptanuclear 3d-4f cluster complexes are ferromagnetic: one exhibits a large magnetocaloric effect while the other a magnetic relaxation behavior, depending on the lanthanoid ions used.     

Synthesis, crystal structure, and magnetic properties of two 3d-4f heterometallic coordination polymers

Two new 4f-3d heterometallic coordination polymers, [Gd₂^IIICo^II(pydc)₃(ox)(H₂O)₄)·2H₂O] (1) and [Dy^IIICu^II(pydc)₂(ox)_1/2(H₂O)₂·H₂O] (2) (pydc = pyridine-2,5-dicarboxylate anion, ox = oxalate dianion) were successfully synthesized under hydrothermal condition. Structure and magnetism of the two coordination polymers were characterized by single crystal X-ray diffraction and Quantum Design (MPMS) SQUID magnetometer. In both compounds, metal centers were connected by double ligand bridges. In 1 the gadolinium ions were linked in sheets by OCO ligand bridges and these sheets were connected by separated cobalt coordination spheres to generate the overall 2-D structure. In 2 the dysprosium centers were constructed into one dimensional chain by OCO bridges from pydc ligand bridges and these chains were linked by oxalate bridges to form sheets and different sheets were connected by copper coordination planes. The copper centers in 2 were linked in chain by elongated OCO brides and the chains were connected by hydrogen bond to generate 3-D structure. Magnetic properties of the two complexes were investigated by variable temperature magnetic susceptibility. The magnetic data suggest that overall antiferromagnetic interactions are present in the two compounds.     

Anion-dependent construction of two hexanuclear 3d-4f complexes with a flexible Schiff base ligand

Two hexanuclear 3d-4f Ni-Eu and Cu-Eu complexes [Eu(4)Ni(2)L(2)(OAc)(12)(EtOH)(2)] (1) and [Eu(4)Cu(2)L(2)(OAc)(12)]·2H(2)O (2) are reported which are formed from the salen type Schiff-base ligand H(2)L (H(2)L = N,N'-bis(3-methoxysalicylidene)butane-1,4-diamine). In both complexes, four Eu(3+) cations are bridged by eight OAc(-) groups and the chain is terminated at each end by two ML (M = Ni and Cu) units. The structures of 1 and 2 were determined by single crystal X-ray crystallographic studies and the luminescence properties of the free ligand and metal complexes in solution were measured.     

3d-4f异金属修饰的缺位Lindqvist型同多酸化合物的合成与表征

在水热条件下,成功合成了一例新的异金属修饰的有机-无机杂化型多金属同多酸簇合物[Cu(en)_2(H_2O)]_4[Ce(W_5O_(18))_2]·4H_2O(1)(en=乙二胺),采用X射线单晶衍射、元素分析、X射线粉末衍射及热重分析对化合物进行了结构分析和基本表征.化合物1属于单斜晶系,P2_1/c空间群,单胞参数为a=2.736 1(2)nm,b=1.452 52(7)nm,c=1.634 53(9)nm,β=97.153(6)°.结构解析表明,化合物1中的中心离子Ce~(4+)与两个同多酸簇块的O原子结合形成八配位的四方反棱柱体,并通过游离的及支撑的[Cu(en)_2(H_2O)]~(2+)进行修饰.值得注意的是,化合物1是首例基于{W_5O_(18)}型同多酸簇块的Cu-Ce异金属修饰型有机-无机杂化的孤立结构.     

A new polyoxometalate-based 3d-4f heterometallic aggregate: a model for the design and synthesis of new heterometallic clusters

A new polytungstoarsenate-based 3d-4f heterometallic aggregate has been synthesized, consisting of three {alpha-AsW10 O 38} fragments bridged by three {Fe-(mu3-O)3-Ce} heterometallic clusters.     

Synthesis, Crystal Structure and Properties of a New One-Dimensional 3d-4f Compound

Introduction Recently cyano bridged 3d-4f heterometallic compounds have attracted much attention because of their interesting structures and magnetic characteristics.1 The most successful and often the sole strategy for preparing these materials consists in assembling two building blocks that are transition and lanthanide metal complexes, one with terminal ligands that are able to act as bridging ligands and the other with available co-ordination sites. The [M(CN)4]2- (M=Ni, Pd, Pt),1f,2 [M…     

A series of 3d-4f heterometallic frameworks comprising 2D lanthanide-organic layers and diverse Cu-complex pillars

Six novel 3D layer-pillared lanthanide-transition metal coordination polymers,LnCuX(IN)2(Ac)(H2O)(Ln = Tb,X = Br(1);Ln = Er,X = Cl(2)),[LnCuCl(IN)2(Ac)].H2O(Ln = Gd(3);Ln = Eu(4)),and [LnCu2Br2(IN)2(Ac)(H2O)].nH2O(Ln = Dy,n =0(5);Ln = Gd,n = 0.5(6))(IN = isonicotinate,Ac = acetate),have been obtained by linking Ln-organic layers and diverse Cu-complex pillars under hydrothermal conditions.1 and 2 are isostructural and formed by 2D Ln-IN-Ac layers and CuX(IN)2 pillars(X = Br(1),X= Cl(2));3 and 4 are isomorph...     

Synthesis,Structure and Characterization of a 3d-4f Hetero-metallic Complex Based on Imidazole-dicarboxylate

A new 3d-4f polymer formulated as {[Sm Co2(μ2-Hmimda)3(μ2-H2mimda)·4H2O]· 3H2O}n(H3mimda = 1-H-2-methyl-4,5-imidazole-dicarboxylic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis,X-ray single-crystal diffraction and magnetic susceptibility measurement.It crystallizes in monoclinic system,space group C2/c,with a = 17.251(6),b = 16.965(6),c = 14.668(5) ?,β = 118.565(5)?,Z = 4,V = 3770(2) ?3,F(000) = 1984,the final R = 0.0597 and w R = 0.1820.In the crystal,the dicarboxylate ligand links the Sm(ⅡI) and Co(Ⅱ) ions to give rise to a heterometallic [Sm Co2(μ2-Hmimda)3(μ2-H2mimda)] aggregate which acts as the second building unit.Then,the SBUs further extended a 2D corrugated layer with a(4,4) topology.The title complex displays strong photoluminescence in the solid state.     

A family of three-dimensional 3d-4f and 4d-4f heterometallic coordination polymers based on mixed isonicotinate and 2-sulfobenzoate ligands: syntheses, structures and photoluminescent properties

Hydrothermal reactions of isonicotinic acid (Hina), 2-sulfobenzoic acid (H(2)sba), d-block metal salts and lanthanide oxides/hydroxides yielded 17 three-dimensional (3D) 3d-4f and 4d-4f heterometallic coordination polymers (HCPs). They are formulated as [LaAg(sba)(ina)(2)](n) (1), [Ln(2)Ag(2)(sba)(2)(ina)(4)(H(2)O)(2)](n) [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9), Er (10)] and [Ln(2)Cu(2)(sba)(2)(ina)(4)(H(2)O)(2)](n) [Ln = La (11), Pr (12), Nd (13), Sm (14), Eu (15), Gd (16), Tb (17)]. Their structures were characterized by single crystal X-ray diffraction, powder X-ray diffraction (XRD), infrared (IR) spectroscopy, elemental analysis (EA), and thermogravimetric analysis (TGA). It reveals that they represent two structural types of 3D HCPs. Furthermore, the investigations of their solid-state photoluminescent (PL) property demonstrate the extraordinary emission behaviors. HCP 1(La-Ag) exhibits tunable blue-to-green PL emissions by variation of excitation light. HCPs 6(Gd-Ag), 11(La-Cu), 12(Pr-Cu) and 16(Gd-Cu) show d(10)-metal-based ligand-to-metal charge transfer (LMCT) or metal-to-ligand charge transfer (MLCT) emissions. HCPs 3(Nd-Ag), 4(Sm-Ag), 5(Eu-Ag), 7(Tb-Ag), 8(Dy-Ag), 13(Nd-Cu), 14(Sm-Cu), 15(Eu-Cu) and 17(Tb-Cu) display characteristic PL emissions of the corresponding Ln(III) ions, while both d(10)-metal-based and 4f-metal-centered emissions are observed in the emission spectra of 4(Sm-Ag), 8(Dy-Ag), 14(Sm-Cu) and 17(Tb-Cu).     

The search for 3d-4f single-molecule magnets: synthesis, structure and magnetic properties of a [Mn(III)2Dy(III)2] cluster

Tetranuclear [Mn(III)2Ln(III)2] complexes formed using tripodal ligands display frequency dependent out-of-phase ac susceptibility signals and temperature and sweep rate dependent hysteresis loops.     

Spontaneous resolution and absolute chiral induction of 3d-4f heterometal-organic frameworks from achiral precursors

The asymmetric assembly and spontaneous resolution of chiral heterometal-organic frameworks from achiral precursors remain a great challenge. Herein, we report the formation and spontaneous resolution of three-dimensional(3 D) chiral 3 d-4 f heterometal-organic frameworks from achiral ligands in the presence of lactic acid enantiomers as chiral inducers. In the absence of a chiral inducer, the reactants randomly generated both enantiopure crystals in equal measure. However, enantiopure lactic acid induced asymmetric resolution to achieve single chiral crystallization. DFT theoretical calculations showed that the absolute chiral resolution of the enantiomers is due to the difference in the interactions between the two enantiomeric Λ/Δ-[Fe L3]3-units and the chiral inducer.     

Synthesis and structural characterization of a novel two-dimensional 3d-4f heterometallic coordination framework based on pentanuclear lanthanide cluster

A novel 3d-4f heterometallic coordination polymer, {[Tm₅(μ₃-OH)₂(BDC)₆(IN)₂Cu(H₂O)₂]·(H₂O)₃}_n (1) [BDC = benzene-1,2-dicarboxylate, IN = isonicotinate], has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. The compound crystallizes in monoclinic system, space group P2₁/c (No. 14), a = 13.7302(5) Å, b = 23.5428(3) Å, c = 21.5789(2) Å, β = 91.491(3)°, V = 6973.0(3) ų, and Z = 4. The structure exhibits unusual two-dimensional Tm-carboxylate layer, which is constructed from the expansion of novel pentanuclear {Tm₅} clusters. More interestingly, the heterometallic Cu(I) ions were successfully planted into such Ln-carboxylate layer by the bifunctional IN bridging ligands, resulting in the formation of an unprecedented 2D heterometallic lanthanide-transition-metal framework.