4f Heterometallic Coordination Polymers Research Articles

Syntheses, Crystal Structures, Magnetic and Near-infrared Luminescence Properties of 3d−4f Coordination Polymers Cu2Pr2, Cu2Eu2 and Cu4Tb2

Three new 3d−4f heterometallic coordination polymers(CPs), namely, [Pr2(CuL)2(nipt)3(H2O)]·2H2O (Cu2Pr2, 1), [Eu2(CuL)2(nipt)3(H2O)]·2H2O(Cu2Eu2, 2) and [Tb2(CuL)4(nipt)3]·8.3H2O(Cu4Tb2, 3)(CuL, H2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; nipt2-=5-nitroisophthalate) were obtained by a solvothermal method and structurally characterized by single-crystal X-ray diffraction analyses, elemental analyses, Fourier transform infrared spectra and ultraviolet visible absorption spectra. In Cu2Pr2 and Cu2Eu2, μ3-bridged and μ5-bridged nipt2- ligands alternately linked three Ln3+ and five metal ions(three Ln3+ and two Cu2+ ions) to generate a 2D heterometallic framework with 3,3,4,5-connected (3.4.5)(32.42.5.63.72)(42.63.8)(42.6) topology. In Cu4Tb2, μ2-bridged and μ4-bridged nipt2- ligands alternately connected two Tb3+ and four metal ions(two Tb3+ and two Cu2+ ions) by carboxylating into a corrugated heterometallic 2D layer with 3-connected (63) topology. The magnetic properties of Cu2Pr2 and Cu2Eu2 were also discussed, the results show that both CPs have a weak antimagnetic interaction. Moreover, the near-infrared luminescence properties of Cu2Pr2 and Cu2Eu2 were also studied.

Synthesis, Crystal Structures and Magnetic Properties of Carboxyl Bridged 3d–4f Heterometallic Coordination Polymers Based on Metalloligand and Lanthanide Ions

Two new three-dimensional 3d–4f heterometallic coordination polymers, {[Tb2(DMSO)6][LCu]3·5CH3OH}n1 and {[Er2(DMSO)4][LCu]3·2DMSO·6CH3OH}n2 (DMSO = dimethyl sulfoxide), based on carboxyl-containing metalloligand LCu ([Cu(2,4-pydca)2]2−, 2,4-pydca = pyridine-2,4-dicarboxylate) and lanthanide ions (TbIII, ErIII), have been synthesized with inter-diffusion method and well characterized. Single-crystal X-ray diffraction studies indicates that 1 and 2 crystallize in the space group of P − 1 of the triclinic crystal system and show 3D frameworks, which are severally established by {Tb2} and {Er2} clusters bridging with LCu metalloligands. The whole frameworks of 1 and 2 illustrate the similar 6-connected single-nodal topology with the point symbol of {412·63}. The most structural difference between two coordination polymers is that 2 exhibits a twofold interpenetrated framework. Thermal analysis reveals that 1 and 2 have similar thermal behavior with the skeleton both collapse after 292 °C. Magnetic measurements suggest that 1 and 2 exhibit the weak antiferromagnetic properties, which may be due to the existence of crystal-field effects of LnIII ions and the contribution of orbital couplings between the spin centers.

Assembly of a New 2D Heterometallic 3d–4f Coordination Polymer Bearing Planar Tetranuclear Square Building Blocks

A new two-dimensional (2D) 3d–4f heterometallic coordination polymer, which is {[Tb2Zn4(µ3-TFMIDC)4(µ4-HTFMIDC)(H2O)8]·2H2O}n, has been successfully synthesized by the solvothermal reaction of 2-(trifluoromethyl)-1H-4,5-imidazole dicarboxylic acid (H3TFMIDC) with Zn(II) and Tb(III) ions. The title compound was structurally characterized by diverse characterization techniques including single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Single-crystal structure analysis reveals that the as-preprared compound is a 2D heterometallic 3d–4f coordination network based on interesting planar tetranuclear squares [Zn4(TFMIDC)4] as building blocks, representing the first example of novel heterometallic coordination polymer based on the H3TFMIDC ligand. In addition, the title compound exhibits very intense green luminescence and characteristic transitions of the Tb(III) ion when excited at 291 nm. Lattice parameters for the title compound: a = 11.1449(12) A, b = 12.8498(13) A, c = 37.553(4) A, α = β = γ = 90°, V = 5378.0(10) A3, Z = 4. A unique 2D 3d–4f heterometallic coordination polymer containing interesting planar tetranuclear square building blocks has been constructed by the solvothermal reaction of 2-(trifluoromethyl)-1H-4,5-imidazole dicarboxylic acid (H3TFMIDC) with Zn(II) and Tb(III) ions.

Syntheses, Structures, and Magnetic Properties of Two Series of 3d–4f Heterometallic Coordination Polymers Derived from Pyrazine‐2,3‐dicarboxylic Acid

Twenty 3d–4f heterometallic coordination polymers (CPs), namely, [Ln2Co(2,3‐pzdc)4(H2O)6]·2H2O [Ln = La (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7)], [Ln2Co(2,3‐pzdc)4(H2O)4]·4H2O [Ln = Dy (8), Er (9)], [Ln2Cu(2,3‐pzdc)4(H2O)6]·2H2O [Ln = La (10), Pr (11), Nd (12), Sm (13), Eu (14), Gd (15), Tb (16)], [Dy2Cu(2,3‐pzdc)4(H2O)4]·4H2O (17), and [Ln2Cu(2,3‐pzdc)4(H2O)4]·2H2O [Ln = Er (18), Yb (19), Lu (20)], are synthesized successfully by the reactions of 2,3‐H2pzdc with LnCl3·nH2O/Ln(NO3)3·nH2O and Co(NO3)2·3H2O/CuCl2·2H2O under hydrothermal conditions. CPs 1–20 are isostructural, and only the coordination and interstitial water molecules, as well as the coordination numbers of LnIII, are different from each other. In 1–20, the 2,3‐pzdc anions link the CoII/CuII and LnIII ions by two coordination modes to form a three‐dimensional (3D) framework with a 3,3,4,4‐connected (4·62)2(42·62·82)(63)2(65·8)2 topology. CPs 6 and 7 manifest the weak ferromagnetic interactions between CoII and LnIII in the low‐temperature range. CP 8 exhibits a field‐induced slow magnetic relaxation behavior. CP 16 shows a magnetic transition between short‐range ferromagnetic ordering at 60 K and long‐range ferromagnetic ordering below 26 K. CP 17 displays field‐induced single‐molecule magnet (SMM) behavior, with a Ueff value of 102.4 K.

Two dimensional porous 3d–4f heterometallic coordination polymers constructed by pyridine-2,3-dicarboxylic acid

Four porous CoIIILnIII 3d–4f heterometallic coordination polymers constructed by the pydcH2 ligand were hydrothermally synthesized and characterized. The adsorption and catalytic properties of compound CoIIIDyIII were investigated.

Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

Synthesis, structure, photoluminescence and magnetism of 3d–4f heterometallic coordination polymers bearing benzimidazole-5,6-dicarboxylate

Hydrothermal reaction of rare earth oxides with 1H-benzimidazole-5,6-dicarboxylic acid (H3bidc) and MnSO4·H2O afforded a series of new three-dimensional (3D) coordination polymers, namely, [Ln2Mn(Hbidc)2(SO4)2·8H2O]n (Ln=Sm (1), Eu (2), Tb (3), Dy (4) and Ho (5)) and [Gd2Mn(Hbidc)2(SO4)2·7H2O]n (6). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, FT-IR, powder X-ray diffraction and thermogravimetric analyses (TGA). The single-crystal X-ray diffraction analysis reveals that coordination polymers 1–6 have similar 3D frameworks fabricated through Hbidc2− and SO42− bridging dinuclear lanthanide secondary building units. Moreover, the photoluminescence of complexes 1–4 and magnetism of complexes 4 and 6 have been investigated, 4 exhibits remarkably slow magnetic relaxation behavior with the energy barrier ΔE/kB=83.3K.

A CuII–GdIII–CuII heterometallic coordination polymer constructed by gadolinium(III) ion and copper(II) Schiff-base building block: Structure and magnetic property

A new 3d–4f heterometallic coordination polymer [Gd(H2O)3(NO3−)(CuL)2] H2O (1) (H3L=glycylglycine, N-[1-(2-hydroxy, phenyl)-propylidene]) has been synthesized and characterized by IR, elemental analysis, TGA and X-ray single-crystal diffraction. In the coordination polymer, two metallo-ligand CuLs are connected with Gd3+ ion to form a 1-D chain via carboxylate and carbonyl oxygen. The neighboring Cu–Gd–Cu chains are further connected by hydrogen bonds to form a two-dimensional structure. Magnetic studies for 1 reveal that ferromagnetic interactions (JCuGd=1.30cm−1) between Cu(II) and Gd(III) centers are operating within the CuII–GdIII–CuII systems.

Synthesis and magnetic properties of a 3d–4f heterometallic chain

A new 3d–4f heterometallic coordination polymer: [MnIIGd2III(OAc)8(H2O)4]·6H2O (1) (OAc−=acetate), has been conventionally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. In 1, two Gd3+ and one Mn2+ cations are linked by carboxylic bridge of OAc− anions, giving a 1D 3d–4f heterometallic [MnIINd2III(OAc)8(H2O)4] chain. In the chain, there exist the short distances between the adjacent Gd(III) and Mn(II) ions as well as Gd(III) and Gd(III) ions, which make this 1D polymer displaying interesting magnetic properties.

Synthesis, structure characterization, and luminescent properties of two novel three-dimensional 4d–4f Ln–Ag coordination polymers based on two mixed ligands and zigzag [Ln2]n chains (Ln = Eu and Ho)

Two original three-dimensional (3-D) 4d–4f heterometallic coordination polymers, [Ln2Ag3(IN)5(OH)2(NO3)][NO3]·nH2O (Ln=Eu, n=2 (1); Ln=Ho, n=1 (2); HIN=isonicotinic acid), have been synthesized by hydrothermal assemble of Ln2O3 (Ln=Eu for 1; Ho for 2), HIN, AgNO3 and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, and thermogravimetric analysis (TGA). These two compounds show isostructural architectures and exhibit unusual 3-D open frameworks which are built upon the second ligand NO3- linking 2-D double wave-like [Ln2Ag2(IN)4(OH)2]n layers and Ag(IN) subunits. 1-D channel is found in the framework. And the luminescent properties of the two compounds have also been investigated.

An intriguing 4d–4f heterometallic coordination polymer with 1D pseudo-nanotube architectures

Abstract A new one-dimensional (1D) 4d–4f heterometallic coordination polymer [ErAg(Himdc)2(H2O)3] (1) (H3imdc = 4,5-imidazoledicarboxylic acid) is synthesized under hydrothermal condition and characterized by elemental analysis, IR, PXRD and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P-1, showing a 1D metal–organic pseudo-nanotube with a 4.014 × 12.027 A2 cross-section. Furthermore, it assembles into a 3D supramolecular architecture via hydrogen bonds between pseudo-nanotubes. The complex 1 exhibits solid-state photoluminescence and high thermal stability.

Syntheses, structures and luminescence of a series of 4d–4f heterometallic coordination polymers constructed by 4,4′-oxybis(benzoicacid)

A series of Ln(III)-Ag(I) 4d–4f heterometallic coordination polymers [LnAg(oba) 2 (H 2 O)] n (Ln = Dy 1 , Ho 2 , Er 3 ) have been synthesized under hydrothermal reactions of 4,4′-oxybis(benzoicacid) (H 2 oba) with Ln(NO 3 ) 3 · 6H 2 O and AgNO 3 at 180 °C. All complexes are isostructural with 3D networks expanded from 1D zigzag chains and 2D layers. In addition, the luminescent property of compound 1 was investigated in the solid-state at room temperature. The coordination mode of H 2 oba ligand. • A series of Ln(III)-Ag(I) 4d-4f heterometallic polymers have been synthesized. • They are the first 4d-4f heterometallic polymers built by 4,4’- oxybis (benzoicacid). • The luminescent property of polymer 1 was investigated in the solid-state.

Two new 2p–3d–4f heterometallic coordination polymers based on 3,5-pyrazoledicarboxylic acid: synthesis, crystal structures and magnetic properties

Abstract Two new 2p–3d–4f heterometallic coordination polymers, [NaCuGd(pdc)2(H2O)7 ∙ 2H2O]n (1) and [NaCuEu(pdc)2(H2O)7 ∙ 2H2O]n (2), have been synthesized based on 3,5-pyrazoledicarboxylic acid (H3pdc). Single-crystal X-ray diffraction analysis reveals that complexes 1−2 are isostructural and both of them display an infinite two-dimensional brickwall-like layer structure consisting of three metal ions and bridged pyrazoledicarboxylate ligands. Magnetic properties of the complexes have been investigated in detail. Furthermore, free-ion approximation was used to fit the magnetic data and a good theory-experiment agreement was obtained for both 1 and 2.

Synthesis, Crystal Structure, Luminescence, and Magnetic Properties of a New 4d–4f Heterometallic Architecture Based on Pyridine-3,4-Dicarboxylic Acid

A 4d–4f heterometallic coordination polymer, [AgEu(pydc)2]·2H2O (1) (H2pydc = pyridine-3,4-dicarboxylic acid), has been synthesized under hydrothermal conditions, and further characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 features a three-dimensional framework containing one-dimensional (1D) channels occupied by free water molecules, which is constructed from 1D inorganic heterometallic chains and linear pydc linkers. After removal of the water molecules from complex 1, the remaining material has high thermal stability. Moreover, the photoluminescence, and magnetic properties of 1 were also investigated.

Six new 3d–4f heterometallic coordination polymers constructed from pyrazole-bridged CuIILnIII dinuclear units

Reactions of lanthanide chlorides, copper hydroxycarbonate and 3,5-pyrazole dicarboxylic acid (H3pdc) under hydrothermal conditions result in six new 3d-4f heterometallic coordination polymers with two types of structures. Compounds [CuLn2(pdc)2(Hpdc)(H2O)4]·2H2O (Ln = Tb (1), Dy (2), Er (3), and Y (4) exhibit a layered porous structure, made up of Cu(II)Ln(III) di-nuclear units which are connected by protonated Hpdc(2-) ligand, while the others [Cu3Ln4(pdc)6(H2O)8] (Ln = Eu (5), Gd (6)) display a three-dimensional (3-D) framework structure, in which six Cu(II)Ln(III) di-nuclear units are cross-linked by two coordinated lanthanide atoms. The catalytic properties of 3 are investigated showing its activity and recyclability in the reaction of cyclopropanation of styrene.

Synthesis and structural characterization of 3d–4f heterometallic coordination polymers: from cluster to chain

Two new 3d–4f heterometallic coordination polymers, [MnIV2CeIV3O6Na(OAc)8(H2O)5](OH)·10H2O (1) and [MnIINdIII2Na2(OAc)8(H2O)6]·2(OH) (2) (OAc− = acetate), have been conventionally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. In 1, three Ce4+ and two Mn4+ cations are bridged by OAc− and μ3-O2− bridges forming a pentanuclear 3d–4f heterometallic [MnIV2CeIV3O6(OAc)8(H2O)5] cluster, while in 2, two Nd3+ and one Mn2+ cations are linked by carboxylic bridge of OAc− anions giving a 1D 3d–4f heterometallic [MnIINdIII2(OAc)8(H2O)6] chain. Additionally, pentanuclear heterometallic [MnIV2CeIV3O6(OAc)8(H2O)5] clusters in 1 are further connected by Na+ cations to result in a 1D chain, whereas the 3d–4f heterometallic chains in 2 are linked by Na1–O–Na1 dimers into a 2D array. Moreover, the variable magnetic susceptibilities of 1 and 2 are investigated.

3d–4f Heterometallic coordination polymers constructed by tetranuclear lanthanide-based cluster as secondary building unit

Four novel 3d–4f heterometallic coordination polymers [Dy4Mn(PDA)6(SO4)2 (H2O)4]·13H2O (1) and [Ln4M(PDA)4(SO4)2(INA)2(H2O)8]·5H2O [Ln = Gd, M = Mn (2); Ln = Eu, M = Zn (3); Ln = Tb, M = Zn (4); PDA = pyridine-2,6-dicarboxylate; INA = isonicotinate] have been hydrothermally synthesized and structurally characterized. Compound 1 possesses a 1D chainlike structure with the tetranuclear [Dy4(PDA)6(SO4)2(H2O)2] “metalloligand” linking the adjacent Mn atoms. Compounds 2–4 are isostructural and possess a 2D heterometallic layer network with a (4,4) connected topology. Furthermore, the magnetic and luminescent properties of compounds 1–4 were investigated.

Series of novel 3D microporous heterometallic 3d–4f coordination frameworks with (5,6)-connected topology: synthesis, crystal structure and magnetic properties

The hydrothermal reaction of rare earth nitrates, CuCN, 1H-1,2,3-triazole-4,5-dicarboxylic acid (H3tda), and isonicotinic acid (Hina) resulted in the formation of a new series of 3d–4f heterometallic coordination polymers [LnCu(tda)(ina)2(H2O)]·3H2O (Ln = Eu (1), Tb (2), Gd (3), Dy (4), Ho (5)], H3tda = 1H-1,2,3-triazole-4,5-dicarboxylic acid, Hina = isonicotinic acid). Complexes 1–5 are isostructural and structurally characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis reveals that the metal cations in these compounds are firstly interconnected by H3tda ligands to produce a carpet-shaped heterometallic ring [Ln2(tda)2Cu4], and then pillared by bridging Hina molecules to form the 3D layer-pillared porous Ln(III)–Cu(II) heterometallic coordination polymers. In addition, the magnetic properties of 1–5 were also investigated in detail.

A new family of 3d–4f heterometallic coordination polymers assembled with 1H-1,2,3-triazole-4,5-dicarboxylic acid: syntheses, structures and magnetic properties

Five isostructural copper(II)–lanthanide(III) heterometallic coordination polymers (CPs), {[Cu2Ln(TDA)2Cl(H2O)4]·2H2O}n [Ln = Gd (Cu–Gd), Tb (Cu–Tb), Dy (Cu–Dy), Ho (Cu–Ho) and Er (Cu–Er)] (H3TDA = 1H-1,2,3-triazole-4,5-dicarboxylic acid), have been synthesized under solvothermal conditions and structurally characterized in detail. In these CPs, two neighboring Cu(II) ions are connected via one μ2-Cl to form [Cu2Cl]3+ units, which are further linked into a copper chain through bridging TDA3−. The neighboring copper chains are further connected by lanthanide to form a two-dimensional structure with sql topology. The magnetic properties of the five isostructural heterometallic CPs have been studied as well.

Three 3d–4f heterometallic coordination polymers based on polydentate ligand and sulfate: Synthesis, crystal structure and photoluminescent properties

Abstract Three heterometallic coordination polymers [Gd 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 1 ), [Eu 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 2 ), and [Dy 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 3 ) (H 3 bidc = 1 H -benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions. They are characterized by elemental analysis (EA), infrared (IR) spectroscopy, thermogravimetric analysis (TGA), single crystal X-ray diffraction, and power X-ray diffraction (XRD). The results reveal that all complexes present almost identical three-dimensional (3D) PtS topology framework structures. The photoluminescent properties of 2 and 3 are investigated.