Xiao-Qing Zhao

A purely lanthanide-based complex exhibiting ferromagnetic coupling and slow magnetic relaxation behavior.

Two lanthanide-organic frameworks, {Ln(TDA)(1.5)(H(2)O)(2)}(n) [TDA = thiophene-2,5-dicarboxylic acid anion; Ln = Gd (1), Dy (2)], were structurally and magnetically characterized. The magnetic studies revealed that the ferromagnetic coupling existed between adjacent lanthanide ions in 1 and 2, and only 2 displays slow magnetic relaxation behavior with tau(0) = 2.4 x 10(-8) s and DeltaE/k(B) = 44.2 K. To our knowledge, it is rather rare that ferromagnetic coupling and slow magnetic relaxation coexist in three-dimensional lanthanide-based frameworks.

3 D MOFs Containing Trigonal Bipyramidal Ln5 Clusters as Nodes: Large Magnetocaloric Effect and Slow Magnetic Relaxation Behavior

Two 3D heterometal-organic frameworks based on infrequent trigonal bipyramidal Ln(5)  clusters as nodes were structurally and magnetically characterized (Ln=Gd (1), Dy (2)). The results indicate large MCE of up to 30.7 J kg(-1)  K(-1) in 1 and slow magnetic relaxation behavior in 2. Expectedly, constructing 3D MOFs based on multinuclear clusters as nodes may will be a new strategy for achieving large -ΔS(m). Additionally, compound 1 exhibits high thermal and solvent stabilities, providing a favorable foundation for realistic applications.

Synthesis, structures, and luminescent and magnetic properties of Ln-Ag heterometal-organic frameworks.

A series of Ln-Ag heterometal-organic frameworks based on 4-hydroxylpyridine-2,6-dicarboxylic acid (H(3)CAM) with formulas {LaAg(2)(CAM)(HCAM)(H(2)O)(2)}(n) (1), {LnAg(HCAM)(2)(H(2)O)(3)}(n) (Ln = Pr, 2; Nd, 3; Sm, 4; Eu, 5), and {LnAg(3)(CAM)(2)(H(2)O)}(n) (Ln = Gd, 6; Tb, 7; Dy, 8; Tm, 9; Yb, 10), have been synthesized with the hydrothermal reaction of Ln(OH)(3), Ag(2)O, and H(3)CAM at 160 degrees C. The single-crystal X-ray diffraction analyses reveal that three kinds of structures are exclusively governed by the size of lanthanide ions and the progression of structures is mainly ascribed to the lanthanide contraction effect. Compound 1 consists of a 3D network with an alpha-polonium-like Ag(+)-homometallic net and helical La(3+) chain. Compounds 2-5 display a 2D honeycomb-like structure with 18-membered Ln(3)Ag(3)O(12) motifs, and compounds 6-10 can be described as a sandwich-like 3D framework built of a 3D Ag(+)-homometallic net and 2D Ln(3+)-4(4) layer. In 4 (Sm), 5 (Eu), 7 (Tb), and 8 (Dy) samples, the efficient energy transfer from CAM to Ln(III) ions was observed, which results in the typical intense emissions of corresponding Ln(III) ions in the visible region, and the strongest emissions are (4)G(5/2) --> (6)H(7/2) (602 nm), (5)D(0) --> (7)F(2) (614 nm), (5)D(4) --> (7)F(5) (548 nm), and (4)F(9/2) --> (6)H(13/2) (576 nm) transitions. Variable-temperature magnetic susceptibility measurements of 6-10 show that the ferromagnetic interaction between gadolinium(III) ions appears in 6, whereas the mu(eff) values of 7-10 smoothly decrease on cooling. For the orbital contribution of Ln(III) ions, it is very difficult to determine the intrinsic magnetic interactions between Ln(III) ions.

Structures and luminescent properties of a series of Ln–Ag heterometallic coordination polymers

Eight new 4f–4d heterometallic coordination polymers have been synthesized using pyridine-2,6-dicarboxylic acid (H2PDA) as ligand under hydrothermal conditions. {[PrAg(PDA)2(H2O)3]·2.5H2O}n (1) comprises a 2D grid-like net, and the grid structure is assembled through a Pr4Ag2 motif as the building block. The subsequent six complexes [LnAg(PDA)2(H2O)3]·3H2O}n (Ln = Ce3+, 2; Nd3+, 3; Sm3+, 4; Eu3+, 5; Tb3+, 6; Dy3+, 7) are 1D double-chain coordination polymers. In 2–7, the Ln3+ and Ag+ ions are linked by carboxylic O bridges to form the helical chains, while the right-handed and left-handed chains are linked through carboxylic O bridges to form the double-helical chain. Additionally, the lattice H2O molecules linked by hydrogen bonds construct the helical water chain. {[CeAg2(PDA)3(Py)4]·H2O}n (8) (Py = pyridine) contains one Ce4+ ion and displays a 1D wave-like chain, in which partial H2PDA ligands were decomposed to pyridine. Luminescent studies reveal that the emission intensity of 7 significantly increases with the introduction of Mg2+ ions into the system of 7, whereas the addition of other metal ions causes emission intensity to remain the same or even decrease. Therefore, complex 7 may serve as a luminescent probe of Mg2+.

Structures and Magnetic Properties of Ferromagnetic Coupling 2D Ln-M Heterometallic Coordination Polymers (Ln = Ho, Er; M = Mn, Zn)

Four new heterometallic coordination polymers have been successfully synthesized, namely, {[Ho(2)(HCAM)(6)Mn(3)(H(2)O)(12)].17.5H(2)O}(n) (1), {[Er(2)(HCAM)(6)Mn(3)(H(2)O)(12)].17.5H(2)O}(n) (2), {[Ho(2)(HCAM)(6)Zn(3)(H(2)O)(12)].26H(2)O}(n) (3), and {[Er(2)(HCAM)(6)Zn(3)(H(2)O)(12)].26H(2)O}(n) (4) (H(3)CAM = chelidamic acid). X-ray crystallographic studies reveal that coordination polymers 1-4 are isostructural and crystallized in the rhombohedral crystal system, space group R3. These compounds comprise a 2D honeycomb-type framework. A 2D water sheet is first found in 3 and 4, which exhibits a novel topological motif. The magnetic results for 1-4 show that ferromagnetic interactions take place between the Ho(3+)/Er(3+) and Mn(2+) ions within 1 and 2.

From 1D zigzag chains to 3D chiral frameworks: synthesis and properties of praseodymium(III) and neodymium(III) coordination polymers

Reaction of H3TDA with PrIII/NdIII salts resulted in two coordination polymers, [Ln(H2O)4(HTDA)(H2TDA)]·H2O (Ln = Pr(1) and Nd(2), H3TDA = 1H-[1,2,3]-triazole-4,5-dicarboxylic acid), crystallizing in the monoclinic P21/c space group with a one-dimensional zigzag chain structure. The number of ligands and water molecules coordinated to the LnIII ions can be reduced by a hydrothermal method and the products transformed into {[Ln(TDA)(H2O)]·2.5H2O}n (Ln = Pr(3) and Nd(4)), crystallizing in the trigonal P3121 space group with a three-dimensional chiral framework structure. The compounds were characterized by elemental analysis, IR, PXRD, circular dichroism spectra and single crystal X-ray diffraction. The variable temperature magnetic susceptibility studies indicated that there are antiferromagnetic interactions between the LnIII ions in 1–4. Gas sorption and separation were studied as well.

Magnetic Nature of the CrIII-LnIII Interactions in [CrIII 2LnIII 3] Clusters with Slow Magnetic Relaxation

Abstract Two 3d‐4f hetero‐metal pentanuclear complexes with the formula {[CrIII 2LnIII 3L10(OH)6(H2O)2]Et3NH} [Ln=Tb (1), Dy (2); HL=pivalic acid, Et3N=triethylamine] have been produced. The metal core of each cluster is made up of a trigonal bipyramid with three LnIII ions (plane) and two CrIII ions (above and below) held together by six μ 3‐OH bridges. Also reported with this series is the diamagnetic CrIII–YIII analogue (3). Fortunately, we successfully prepared AlIII–LnIII analogues with the formula {[AlIII 2LnIII 3L10(OH)6(H2O)2]Et3NH⋅H2O} [Ln=Tb (4), Dy (5)], containing diamagnetic AlIII ions, which can be used to evaluate the CrIII–LnIII magnetic nature through a diamagnetic substitution method. Subsequently, static (dc) magnetic susceptibility studies reveal dominant ferromagnetic interactions between CrIII and LnIII ions. Dynamic (ac) magnetic susceptibility studies show frequency‐dependent out‐of‐phase (χ′′) signals for [CrIII 2TbIII 3] (1), [CrIII 2DyIII 3] (2), and [AlIII 2DyIII 3] (5), which are derived from the single‐ion behavior of LnIII ions and/or the CrIII–LnIII ferromagnetic interactions.