4f Heterometallic Coordination Polymers Research Articles

Copper(II)–lanthanide(III) coordination polymers constructed from pyridine-2,5-dicarboxylic acid: Preparation, crystal structure and photoluminescence

A series of 3d–4f heterometallic coordination polymers, formulated as {[Cu3Ln2(pydc)6(H2O)12]·4H2O}n [Ln=Tb (1), Eu (2), Dy (3), Ho (4), Lu (5)], {[CuNd2(pydc)4(H2O)3]·H2O}n (6) and {[Cu3Pr2(pydc)6(H2O)13]·4H2O}n (7) (where H2pydc=pyridine-2,5-dicarboxylic acid), have been hydrothermally prepared by reactions of H2pydc ligand with lanthanide ions in the presence of Cu(II) ion. X-ray crystal structure analysis reveals that these compounds exhibit rich structural chemistry. 1–5 are isomorphous and present a two-dimensional network constructed from Ln2Cu2L2(H2O)2 SBU rings and CuL2(H2O) building blocks. In 6, two-dimensional ladder-like layers based on Nd(III) belts and CuL2O2 units are assembled by H2pydc ligands into a three-dimensional open framework. Polymer 7 displays a two-dimensional wave-like layer structure containing two distinct ring units, in which a new coordination mode of the pydc2− ligand is observed. The results indicate that the coordination flexibility of the pydc2− ligand and lanthanide contraction effect play cooperative roles in the formation of coordination polymers with different polymeric architectures. Compounds 1–2 exhibit intense green and red luminescence emission characteristics of Tb(III) and Eu(III), respectively. Furthermore, elemental analyses (EA), infrared spectra (IR) and thermogravimetric analyses (TGA) of these compounds were also studied.

Hydrothermal syntheses and crystal structures of a series of 3d–4f heterometallic tetrazole-based coordination polymers

Abstract A series of novel three-dimensional (3D) Ln(III)–Cu(I) heterometallic tetrazole-based coordination polymers, namely, [LnCu(3-tzba) 2 (H 2 O) 4 ] n [Ln = Ho ( 1 ); Nd ( 2 ); Sm ( 3 ); Pr ( 4 ); 3-tzba = 3-(1 H -tetrazol-5-yl)benzoate], were successfully synthesized through in situ [2 + 3] cycloaddition reaction under hydrothermal conditions. Compounds 1 – 4 are isomorphous 3D coordination frameworks with 1D anionic chains [Ln(3-tzba) 2 (H 2 O) 4 ] − linking the adjacent Cu(I) ions possessing an sql type net with Schlafli symbol (4 4 ). To our best knowledge, they are the first lanthanide-transition heterometal-organic coordination polymers obtained through in situ tetrazole synthesis. In addition, the thermal stability and magnetic property of 1 were also investigated.

Syntheses, crystal structures and physical properties of two unusual 4d–4f heterometallic coordination polymers

Two novel heterometallic coordination polymers, [AgSm(pydc)2]·2H2O (1) and [AgTb(pydc)2]2·H2O (2) (H2pydc=pyridine-3,4-dicarboxylic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complexes 1 and 2 are isomorphous and exhibit 3D open framework heterometallic coordination polymer containing 1D channels occupied by lattice water molecules. To our knowledge, both compounds represent the rare examples of 3D open-framework 4d–4f heterometallic coordination polymers with open framework structure. Moreover, their luminescent and magnetic properties have also been investigated.

A novel two-dimensional 3d–4f heterometallic coordination polymer with (4, 4)-connected topology: Crystal structure, luminescence and magnetic properties

Abstract A novel 3d–4f heterometallic coordination polymer, namely, {[Sm2(PBDA)2·2H2O][Zn2(PBDA)2(Cl)2]}n (1), (H2PBDA = 3 -(pyridin-3-yl-oxy) benzene − 1,2-dicarboxylic acid) has been hydrothermally synthesized by using samarium(III) nitrate, H2PBDA acid and zinc chloride as raw materials, and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. Polymer 1 possesses two-dimensional (2D) network containing the original 1D heterometallic chain composed of [Sm2Zn2(PBDA)2] moieties. Variable temperature magnetic susceptibility studies reveal that 1 displays possible weak antiferromagnetic coupling between the neighboring Sm(III) ions, and the photoluminescent properties of polymer 1 as well as free H2PBDA ligand were also investigated.

A series of 3d–4f heterometallic three-dimensional coordination polymers: syntheses, structures and magnetic properties

Seven lanthanide-cobalt heterometallic three-dimensional coordination polymers: {[Ln(3)Co(2)(BPDC)(5)(HBPDC)(H(2)O)(5)](ClO(4))(2)·mH(2)O}(n) (Ln = Eu (1, m = 10.25), Gd (2, m = 8), Tb (3, m = 9.5), Dy (4, m = 11), Ho (5, m = 10.5), Tm (6, m = 11), Lu (7, m = 10.25); BPDC = 5,5'-dicarboxylate-2,2'-dipyridine anion) were structurally and magnetically characterized. Compounds 1-7 crystallize in the orthorhombic space group Pbca, featuring a 3D sandwich framework. Magnetic properties of 2-6 have been investigated by using DC (direct current) and AC (alternating current) susceptibility measurements. Among these compounds, only compound 4 displays significant frequency dependence, albeit without reaching the characteristic maxima above 2 K, implying slow magnetic relaxation behavior in 4. After the application of a DC field, good peak shapes of AC signals were obtained and the energy barrier ΔE/k(B) = 62.89 K and the preexponential factor τ(0) = 6.16 × 10(-8) s. To our knowledge, 4 has the highest energy barrier in Ln-Co SMM systems hitherto.

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).

A series of 3d–4f heterometallic coordination polymers constructed from size-tunable copper halide clusters and lanthanide-organic motifs

A series of three-dimensional (3D) lanthanide–copper coordination polymers, namely [Ln2(NA)6Cu6Br6(H2O)4]·3.5H2O] [Ln = Sm (1), Eu (2), Tb (3), NA− = nicotinate], [Ln(NA)2Cu2Br2(C2O4)0.5(H2O)2]·2H2O [Ln = Gd (4), Er (5), C2O4 = oxalate], [Ln(NA)2Cu3Br3(OAc)(H2O)] [Ln = Sm (6), Eu (7), Tb (8), OAc = acetate], [Er2(NA)6Cu7Br7(H2O)4]·2H2O (9) and [Gd(NA)3Cu3Cl3(H2O)2]·H2O (10) have been hydrothermally synthesized and structurally characterized. Compounds 1–3 are constructed from Ln–organic chains and two distinct Cu4Br4 clusters possessing a (411.64)2(414.67)2(418.610)(49.6)2 topology. Compounds 4 and 5 are composed of two-dimensional (2D) Ln–organic layers and cubane-like Cu4Br4 clusters possessing a (43.66.8)(43)(46.66.83) topology. Compounds 6–8 can be viewed as the connection between Ln–organic chains and prism-like Cu6Br6 clusters with 4,6T50 topology. Compound 9 is constructed by Er–organic chains and dicubane-like Cu8Br7 clusters possessing a fluorite (flu) topology. Compound 10 consists of Gd–organic chains and inorganic Cu3Cl3 chains with tcj/hc topology. The diversity of the products demonstrates that the auxiliary ligand, pH value, reaction temperature and anion have significant effect on the construction of the structures. Moreover, the photoluminescence of 1–3 and 6–8, and the magnetism of 9 and 10 were investigated.

Two novel 3D 3d–4f polymers with 5-(isonicotinamido)isophthalic acid: Synthesis, structures and properties

Two new 3d–4f heterometallic coordination polymers [Mn0.5Ln(INAIP)2(H2O)2]·2H2O [Ln=Eu (1), Gd (2)] have been prepared by hydrothermal reactions of the corresponding lanthanide salt with 5-(isonicotinamido)isophthalic acid (H2INAIP) in the presence of MnCO3 and NaOH. Both complexes have been characterized by single crystal X-ray diffraction analyses, elemental analyses, infrared absorption spectra, and thermogravimetric analyses. The results of structural analyses show that 1 and 2 are isostructural and feature non-interpenetrated 3D coordination framework containing 2D (4,4) lanthanide–carboxylate layers. They have the same 3D structure with trinodal (3,3,4)-connected new topology net with Point (Schläfli) symbol (83)4(84·102)(86)2. In addition, photoluminescence and magnetic properties were also investigated.

An unusual 3D 3d–4f heterometallic coordination polymer based on the linkages of Sm2(IN)6 pillars and 2D [Cu7Br6]n+ layers: Crystal structure and luminescent property

Abstract An unusual three-dimensional (3D) pillared-layer 3d–4f (Cu+–Sm3+) heterometallic coordination polymer, {Sm2Cu7Br6(IN)7(H2O)5·3H2O}n (1) (HIN = isonicotinic acid), has been successfully synthesized by hydrothermal reaction of Sm2O3, CuBr2, HIN, HClO4 and H2O, and characterized by elemental analyses, IR, PXRD, and single-crystal X-ray diffraction. The structure determination reveals that 1 possesses 3D heterometallic framework constructed upon unprecedented [Cu7Br6]nn+ inorganic layers linked by dimeric Sm2(IN)6 pillars. Additionally, the thermogravimetric analysis and luminescent property of 1 were investigated and discussed.

A Porous 4d–4f Heterometallic Coordination Polymer: Synthesis, Crystal Structure and Physical Properties

AbstractA 4d–4f heterometallic coordination polymer, [AgLa(pydc)2]·3H2O (1) (H2pydc = pyridine‐3,4‐dicarboxylic acid), has been synthesized under hydrothermal conditions, and further characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. Complex 1 features a three‐dimensional (3D) framework containing one‐dimensional (1D) channels occupied by free water molecules, which is constructed from 1D inorganic heterometallic chains and linear pydc linkers. To the best of our knowledge, complex 1 represents a rare example of 3D open‐framework 4d–4f heterometallic coordination polymer. Moreover, after removal of the water molecules from complex 1, the remaining material has high thermal stability and good adsorption behavior towards nitrogen gas.

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

Two new 4f–3d heterometallic coordination polymers, [Gd 2 IIICo II(pydc) 3(ox)(H 2O) 4)·2H 2O] ( 1) and [Dy IIICu II(pydc) 2(ox) 1/2(H 2O) 2·H 2O] ( 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 O C O 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 O C O 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 O C O 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.

Solvothermal synthesis, structure and properties of a new 3-D Cu(I)–Gd(III) heterometallic coordination framework

Abstract A new 3d–4f heterometallic coordination polymer, [CuGd2(INAIP)3(HCOO)(H2O)3]·3H2O (1), [H2INAIP = 5-(isonicotinamido)isophthalic acid] has been synthesized and characterized by single crystal X-ray diffraction analysis. The results of structural analyses show that 1 has a two-fold interpenetrated 3D coordination framework with a rare sqc27 topology. In addition, thermogravimetric and magnetic properties were also investigated.

A series of three-dimensional 3d–4f heterometallic coordination frameworks based on pyridinedicarboxylic acid

Four new 3d–4f heterometallic coordination polymers [Cu3Eu2(2,5-pydc)6(H2O)12]·4(H2O) (1), [Zn2Eu2(2,5-pydc)5(H2O)2]·3(H2O) (2), and [Co3Ln2(2,6-pydc)6(H2O)6]·4(H2O) (Ln = Eu, 3; Dy, 4) (H2pydc = pyridinedicarboxylic acid) have been synthesized and characterized. All of these compounds have extended 3D coordination frameworks containing supramolecular 1D channels, in which lattice water molecules are located. Hydrogen bonds stabilize the 3D frameworks. Additionally, a study of their fluorescence properties has indicated that compounds 1 and 2 show the characteristic transitions of Eu3+. Weak antiferromagnetic interactions are observed in compound 3.

A Series of Three-Dimensional 4d−4f Heterometallic Coordination Polymers with Six-Connected Doubly Interpenetrated pcu Net Topology: Structural, Photoluminescent, and Magnetic Properties

A series of lanthanide(III)-Ag(I) 4d−4f heterometallic coordination polymers (HCPs) with pcu topology, {[LnIIIAgI(Hbidc)(bidc)(ox)0.5(H2O)]·H2O}n (Ln = Sm 1, Eu 2, Gd 3, Tb 4, Dy 5, Ho 6, Er 7, H2bidc =1H-benzimidazole-5,6-dicarboxylic acid, ox = oxalate), have been synthesized through self-assembly reactions. All seven complexes are isostructural and have three-dimensional 2-fold interpenetrated structures, with both the organic ligand and oxalate groups acting as bridges. These new complexes crystallize with the same unique six-connected three-nodal net described by (108·12·164·182) (10)6 topology. The ferromagnetic properties of complex 3 were investigated. Moreover, complexes 1, 2, 4, and 5 exhibit very strong photoluminescence properties and with long lifetimes in the solid state at room temperature.

A novel three-dimensional 3d–4f heterometallic coordination polymer with unique (3,4)-connected topology and helical units: Synthesis, crystal structure and photoluminescence property

One new three-dimensional 3d–4f heterometallic coordination polymer, namely, {[EuZn2(imdc)2(C2O4)0.5(H2O)4]·2H2O}n (1) (H3imdc = imidazole-4,5-dicarboxylic acid), has been successfully synthesized by the hydrothermal reactions of Eu2O3, Zn(NO3)2·6H2O, H3imdc, H2C2O4·2H2O and H2O. Single-crystal X-ray diffraction analysis reveals that complex 1 possesses 3D heterometallic framework containing 2D layer based on L–Zn2–L (L = imdc) helical chains and L–EuZn1–L chains. Complex 1 exhibits unprecedented (3,4)-connected four-nodal topology with Schläfli symbol (6·7·8) (6·7·9) (6·72·82·10) (7·82). Moreover, the photoluminescence property of 1 was investigated in the solid-state at room temperature.

1-D Ln–Ag (Ln = Eu; Tb) heterometallic coordination polymers with pyridine-2,6-dicarboxylate as the single ligand: Synthesis, crystal structures, and luminescence

Two new 4d–4f heterometallic coordination polymers [AgLn(pydc)2(H2O)3] · x(H2O) [Ln = Eu, x = 1.25 (1); Ln = Tb, x = 1.25 (2); pydc = 2,6-pyridinedicarboxylate] have been synthesized and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. Both structures display the same unusual 1-D heterometallic coordination polymer based on Ln building blocks and Ag ions. Thermal stabilities and luminescent properties of 1 and 2 are presented.

Three-dimensional 3d–4f heterometallic coordination polymer containing Sm2Mn4 clusters: Synthesis, crystal structure and properties

Abstract Heterometallic coordination polymers of the form {[SmMn2(imdc)2(OAc)(H2O)]·2H2O}n (1) (H3imdc = 4,5-imidazoledicarboxylic acid, HOAc = acetic acid) were hydrothermally synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The results reveal that 1 has a three-dimensional framework containing Sm2Mn4 clusters. The luminescence and magnetic properties of 1 were also investigated.

3D pillar-layered 4d–4f heterometallic coordination polymers based on pyridine-3,5-dicaboxylate and oxalate mixed ligands

Three 4d–4f heterometallic polymers, Ln 2Ag 2(Hpydc) 2(pydc) 2(ox) · 4H 2O (Ln = Nd ( 1), Eu ( 2) and Er ( 3); H 2Pydc = pyridine-3,5-dicarboxylic acid, H 2ox = oxalic acid), have been successfully synthesized under hydrothermal condition and structurally characterized. Single-crystal X-ray diffraction analyses reveal that three compounds are isomorphous and exhibit 3D pillar-layered coordination frameworks constructed from two-dimensional lanthanide-carboxylate layers and [Ag(pydc)] − pillars. Furthermore, the luminescent property of compound 2 was studied.

Isostructural 3D Ln–Ag (Ln = Eu; Dy; Ho) coordination frameworks based on mixed nicotinate and oxalate ligands: Synthesis, crystal structures and luminescence

By control of mixed organic ligands with different geometries, three unusual 4d–4f heterometallic coordination polymers, [AgLn(nic)2(ox)]·2H2O [Ln=Eu (1); Dy (2); Ho (3)] [nic=nicotinate; ox=oxalate] have been synthesized under hydrothermal reaction. Three structures represent 3D open heterometallic coordination frameworks that are constructed from rare zigzag lanthanide-ox-silver chains and nic linkers. Furthermore, the luminescent property of complex 1 was discussed.

New 3d−4f Heterometallic Coordination Polymers Based on Pyrazole-Bridged CuIILnIII Dinuclear Units and Sulfate Anions: Syntheses, Structures, and Magnetic Properties

A series of 3d−4f heterometallic coordination polymers {[CuLn2(pdc)2(SO4)(H2O)6]·H2O}n (Ln = Tb (1), Dy (2); H3pdc = 3,5-pyrazoledicarboxylic acid), {[CuLn2(pdc)2(SO4)(H2O)4]·H2O}n (Ln = Sm (3), Eu (4), Gd (5), Tb (6), Dy (7)) have been hydrothermally synthesized and structurally characterized. The sulfate anions were in situ obtained from oxidation of CuSCN during the reaction. Complexes 1−7 are all constructed from pyrazole-bridged CuIILnIII dinuclear units and sulfate anions. Complexes 1 and 2 are isostructural and possess an infinite double-stranded tapelike 1D coordination framework. However, complexes 3−7 are interesting 3d−4f heterometallic coordination polymers with similar 3D framework structures. The magnetic properties of compounds 2, 4−6 have been investigated through the magnetic measurements over the temperature range of 1.8−300 K.