3D Heterometallic Coordination Polymers Research Articles

0D to 3D PrIII metal-organic networks crystal engineered for optimal iodine adsorption.

Four new praseodymium(III) metal-organic compounds varying in dimensionality from 0D to 3D have been designed and synthesized based on N-heterocyclic polycarboxylic acids, including pyridine-2,6-dicarboxylic acid (H2pydc) and pyrazine-2,3-dicarboxylic acid (H2pzdc). Altering the concentration of piperazine (pip, ancillary ligand) enables control over the dimensionality of the compound by switching between the 0D [H2pip][Hpip][Pr(pydc)3]·4H2O (I) and the 1D {[Pr(pydc)(Hpydc)(H2O)2]·4H2O}n (II) coordination polymer (CP). Upon replacing H2pydc with H2pzdc, CP II is converted to the 2D CP [Pr(pzdc)(Hpzdc)(H2O)3]n (III) and using the metalloligand [Zn(Hpzdc)2(H2O)2]2-, the 3D heterometallic CP {[Pr2Zn(pzdc)4(H2O)6]·2H2O}n (IV) is formed. Compound IV shows high stability in the absence of uncoordinated solvent molecules and is stable up to 400°C, even in the presence of humidity. Therefore, IV was utilized for iodine adsorption in the vapour phase and in the presence of humidity. The results confirm the remarkable potential of IV for reversible adsorption of iodine vapour.

Solvothermal synthesis, structure and properties of heterometallic coordination polymer based on metalloligand and alkaline-earth metal calcium

A new 3D heterometallic coordination polymer (HCP), which formulated as {[Ca(H2O)2][LCo]·DMSO·2H2O}n (1) (DMSO = dimethyl sulfoxide), has been solvothermally synthesized from metalloligand LCo = [Co(2,4-pydca)2]2– (2,4-pydca = pyridine-2,4-dicarboxylate) and alkaline-earth ion CaII. HCP 1 has been well characterized by Fourier-transform infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. The crystallographic analysis indicates that HCP 1 crystallizes in the monoclinic system with space group of C2 and possesses the 3D framework structure, which is constructed from metalloligands LCo connecting with CaII ions via the carboxyl groups. The 3D framework of HCP 1 can be defined as (4,4,4)-connected 3-nodal topology with the point symbol of {42·84}{42·84}{42·84}. Thermogravimetric analysis exhibits that the skeleton of HCP 1 collapses after 375 °C. Magnetic susceptibility study reveals the presence of antiferromagnetic interaction between the spin centers. The solid-state luminescence property of HCP 1 has also been investigated.

Synthesis, Crystal Structure, and Photoluminescent Properties of a Series of LnIII–CuI Heterometallic Coordination Polymers Based on Cu4I3 Clusters and Ln–ina Rod Units

A novel series of LnIII–CuI heterometallic coordination polymers (HCPs) {[Ln2Cu4I3(ina)7(DMA)2]n·nDMA, Ln = La (1), Ce (2), Pr (3) Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9) Ho (10), Er (11), Yb (12), Hina = isonicotinic acid, DMA = N,N-dimethylacetamide} were synthesised by a solvothermal reaction. The structures of compounds 1–12 were characterised by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Single crystal X-ray diffraction studies revealed that 1–12 are isomorphous and are 3D heterometallic coordination polymers based on inorganic Cu4I3 clusters and Ln2(ina)7(DMA) rod units. In addition, the luminescent properties of compounds 5–9 have been investigated in detail. All of them exhibited green light emission due to the synergistic effects of characteristic emissions of lanthanide ions and iodide-to-copper charge transfer.

Two Novel Fe7Mg8 and Fe8Co7 Cluster-Based 3D Heterometallic Coordination Polymers with H4PMIDA and H3BTC as the Co-ligands: Synthesis, Structures, and Fluorescent Properties

Two novel Fe7Mg8 and Fe8Co7 cluster-based 3D heterometallic coordination polymers, [Fe7Mg8(PMIDA)6(BTC)2(H2O)12]·6H2O(1) and [Fe8Co7(PMIDA)6(BTC)2(H2O)12]·6H2O(2), constructed by multifunctional H4PMIDA (N-(Phosphonomethyl)imino-diacetic acid) and H3BTC(1,3,5-benzenetricarboxylate acid) as the co-ligands, have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR spectrum, powder X-ray diffraction, thermal analysis and single-crystal X-ray diffraction. The complexes 1 and 2 are basically isostructural and feature a cubic 3D open framework constructed by [M15(PMIDA)6(H2O)12]] (M15 = Fe7Mg8 for 1 and Fe8Co7 for 2) heteronuclear clusters and BTC3− ligands. Moreover, the solid-state fluorescence properties of the complexes have also been investigated at room temperature.

Synthesis, Structure, and Luminescence of a New 3D Heterometallic Coordination Polymer Constructed by 2-Hydroxynicotinate

A new heterometallic coordination polymer, namely, [NaZn(Hnic)3] (1), has been synthesized under hydrothermal condition (H2nic = 2-hydroxynicotinic acid). The Hnic ligands bridge Zn(II) and Na(I) atoms to furnish a fascinating 3D framework. The 3D framework is further consolidated by N-H···O hydrogen bonds. In addition, the luminescent property of compound 1 has been studied in solid state at room temperature.

Ionothermal synthesis of a 3D heterometallic coordination polymer based on the rod shaped copper(II)–sodium(I)-carboxylate secondary building units with a pcu topology

Compound [(EEIM)NaCu(phth)2]n (1) (EEIM=1,3-diethylimidazolium and phth=terephthalate) was synthesized by using the mixed ionic liquids of 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM]-BF4 and chiral 1-ethyl-3-methylimidazolium l-lactate as solvent. The sodium(I) ion deriving from the [EMIM]-BF4 with a small amount of Na(I) impurity incorporated into the structure is unprecedented. Compound 1 is a 3D anionic framework based on a unique rod shaped heterometallic copper(II)–sodium(I)-carboxylate secondary building unit, exhibiting a distorted pcu-(412·63) topology. It is interesting that the organic template of [EEIM]+ cation formed from an in situ reaction acting as extraframework charge-balancing species occupies the 1D rhombic channels of the 3D anionic framework. The roles of the ionic liquid in ionothermal synthesis and crystallization of 1 are briefly discussed.

A chiral 2p–3d heterometallic azido complex with 2,6-pyridinedicarboxylate as the co-ligand showing magnetic order

A new chiral 3D heterometallic coordination polymer [NaCo2(L)2(N3)·(MeOH)]∞ (1) (L = 2,6-pyridinedicarboxylate) was synthesized and characterized magnetically. Ferro- and antiferromagnetic interactions co-exist in 1, which results in a magnetic phase transition at the high temperature of 29 K.

Supramolecular Self-Assembly of 1D and 3D Heterometallic Coordination Polymers with Triruthenium Building Blocks

Ru(3)(TSA)(6) (1; H(2)TSA=2-thiosalicylic acid), which bears six peripheral carboxylate groups and was isolated in the form [NEt(4)](1.5)[Ru(3)(HTSA)(2)(TSA)(4)](OAc)(0.5)·3.5H(2)O, serves as a building block for assembly of heterometallic coordination polymers. Treatment of 1 with [Fe(acac)(3)] (acac=acetylacetonate) in EG/H(2)O (EG=ethylene glycol) afforded 1D Ru(3)-Fe coordination polymer 2 by means of the connection of the building block 1 through iron centers. Treatment of 1 with MnCl(2) in EG resulted in the formation of 1D Ru(3)-Mn(3) coordination polymer 3, which features self-assembled polynuclear linking units Mn(3)(OCH(2)CH(2)O)(3), each of which contains a planar Mn(3)O(3) ring. By treating 1 with Gd(NO(3))(3) and NaHCO(3) in EG, a 3D Ru(3)-Gd(6) coordination polymer 4 was obtained; this 3D coordination polymer features unprecedented Gd(6)(μ(3)-CO(3))(4) units. The magnetic properties of 1-4, along with DFT calculations on the electronic structure of 1, are also described.

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 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).

Synthesis, crystal structures and luminescence properties of two novel 3D heterometallic coordination polymers

Abstract Two heterometallic coordination polymers, {KBa(ptc)(H2O)2}n(1) and {KCaEr(ptc)2(H2O)}n(2) (H3ptc = pyridine-2,4,6-tricarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single crystal X-ray diffraction. 1 and 2 exhibit two novel three-dimensional (3D) frameworks, and the luminescence properties of 1, 2 were investigated.

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.

Synthesis, structure and XPS of a novel two-dimensional CuII–EuIII heterometallic–organic framework

Abstract Hydrothermal reaction of Eu2O3, CuI, 2, 2′-bipyridine-5, 5′-dicarboxylic acid and 2, 2′-bipyridine in the presence of ethanol and water affords a new 4f–3d heterometallic coordination polymer {[EuCu(bpdc)2·(H2O)4 I)]·2H2O}n (1), (H2bpdc = 2, 2′-bipyridine-5, 5′-dicarboxylic acid). Compound 1 was structurally characterized by elemental analysis, FT-IR spectroscopy, single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and luminescence measurement. Single-crystal X-ray diffraction analysis reveals that the heterometallic polymer is interconnected by Eu3+ through carboxylic groups to produce a linear 1D structure along a direction, then through Cu2+ chelating double nitrogen atoms of bpdc2− ligand along b direction to form a 2D (two-dimensional) CuII–EuIII heterometallic–organic framework. X-ray photoelectron spectroscopies (XPS) confirm that chemical valences of Eu and Cu are + 3 and + 2 respectively. The fluorescent intensity change between H2bpdc ligand and compound 1 reveals a radical static quenching effect from CuII ions.

Synthesis, crystal structures and properties of Ln(iii)–Cu(i)–Na(i) and Ln(iii)–Ag(i) heterometallic coordination polymers

Nine 3D heterometallic coordination polymers, namely [NaLn2Cu6I5(IN)6(ox)(H2O)4]·H2O [Ln = La (1), Eu (2), Gd (3), Tb (4), HIN = isonicotinic acid, ox = oxalate], [Ln2Ag4(IN)5(ox)2(NO3)(H2O)2]·3H2O [Ln = Dy (5), (6) Ho], [LnAg(IN)2(ox)]·H2O [Ln = La (7), Pr (8), Tm (9)] have been successfully synthesized under hydrothermal conditions. Compounds 1–4 exhibit same unusual 3D pillared-layer heterometallic coordination frameworks that are built up by the Ln-ox-Na layers, 2D inorganic [(Cu6I5)+]n layers and IN ligands. Compounds 5 and 6 represent 3D coordination frameworks that are constructed from rare Ln(III)-ox-IN chains and Ag(I)-IN-ox layers. 3D coordination networks of compounds 7–9 are built up from 2D Ln(III)-IN-ox layers and Ag(I)-IN-ox subunits. Furthermore, the magnetic properties of compounds 5 and 6 and the luminescence properties of compounds 2, 4 and 5 have been investigated.

A new family of 3D heterometallic 3d–4f organodisulfonate complexes based on the linkages of 2D [Ln(nds)(H2O)]+layers and [Cu(ina)2]−chains

Seven novel 3D heterometallic coordination compounds, LnCu(nds)(ina)2·H2O [Ln = Eu (1), Ce (2), Er (3), Gd (4), Sm (5), Tb(6), Dy(7); nds = 2,6-naphthanlenedisulfonate; ina = isonicotinic acid], have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectra, thermogravimetric analysis and single-crystal X-ray diffraction analysis. These compounds are isostructural and constructed by the linkages of 2D [Ln(nds)(H2O)]+ layers and Cu(ina)2− chains, which represent the first examples of 3D heterometallic coordination polymers created by the organodisulfonate ligands. Moreover, the complexes exhibit a novel (3,6)-connected net. The luminescence properties of complexes 1, 5 and 6 and the magnetic property of 4 were also investigated.

A 3D hetero-metallic coordination polymer with an anionic rutile topological net decorated by polymeric cationic chains

The syntheses, X-ray crystal structures and topological analyses of a three-dimensional coordination polymer complex, {Cd(BTC)Na(H2O)3}n 1 (BTC3− = 1,3,5-benzenetricarboxylic anion), are reported. Complex 1 features a hetero-metallic framework built by alkali metal (sodium) and d10 metal (cadmium) with organic BTC. From a topological point of view, the whole structure can be considered as an anionic rtl (rutile) net constructed from Cd2+ and BTC3− decorated by polymeric cationic chains of [Na(H2O)3]n+.

Hydrothermal synthesis, crystal structure and magnetic characterization of two 4f–3d heterometallic coordination polymers

Two new 4f–3d heterometallic coordination polymers [Gd 2Co(L 1) 3(ox)(H 2O) 4]·2.5H 2O ( 1, L 1 = pyridine-2,5-dicarboxylate anion, ox = oxalate dianion) and [GdNi(L 2) 2(ox) 0.5(H 2O) 3]·3H 2O ( 2, L 2 = pyridine-2,3-dicarboxylate anion) were successfully synthesized under hydrothermal conditions. In compound 1, one dimensional heterometallic and lanthanide infinite sheets were constructed with sole L 1 spacers and L 1–ox mixed bridges, respectively. While similar one dimensional heterometallic infinite sheet and normal lanthanide infinite zigzag chain were formed based on sole L 2 and L 2–ox mixed bridges, respectively in compound 2. Both of the two compounds exhibited new and interesting three dimensional topologies. In addition, the magnetic properties of the two compounds were analyzed via solid-state dc magnetic susceptibility measurements.

Crystal structure and magnetic property of a 3D heterometallic coordination polymer constructed by 3-cyanobenzoate and 3-(5H-tetrazol) benzoate ligands

Abstract Hydrothermal reaction of Cd(NO3)2, Co(NO3)2, Na(3-cba) and NaN3 yielded a 3D heterometallic coordination polymer, [Cd(μ5-3-tzba)(μ2-3-cba)(μ3-OH)Co(H2O)]n·2nH2O 1 (3-H2tzba = 3-(5H-tetrazol)benzoic acid and 3-Hcba = 3-cyanobenzoic acid), which was characterized by single-crystal X-ray diffraction. The in situ [2 + 3] cycloaddition reaction of nitrile and azide in presence of Cd(II) salt afforded tetrazolate-based 3-tzba2− ligand. In 1, metal-oxo chains [Cd(μ3-OH)Co]n are linked by 3-tzba2− in an unprecedented μ5-κN1:κN2:κN3:κN4:κO1,O2 coordination mode to form 2D layers, which are further pillared by 3-cba− to generate a 3D open framework encapsulating 1D chiral channels. Variable-temperature magnetic studies show that 1 exhibits antiferromagnetic interactions between Co(II) ions bridged by μ3-OH group.

Synthesis and structure of 3D heterometallic (3d–4f) coordination polymers: {[Ln2Cu(pydc)4(H2O)6]·2H2O} n

Two new 3D heterometallic (3d–4f) coordination polymers {[Ln2Cu(pydc)4(H2O)6]·2H2O}n [Ln = Eu (1) and Gd (2)] have been synthesized by hydrothermal reactions and characterized by elemental analysis, X-ray single-crystal analyses, and IR spectroscopy. X-ray crystal structure analyses show that 1 and 2 possess 3D networks and strong intramolecular hydrogen bonding interactions which was confirmed by thermogravimetric (TG) analysis.

Syntheses and structural characterization of three coordination polymers of Cd(II), Zn(II) and Pb(II) with the “V” shape ligand 4,4′-[isopropylidenebis( p-phenyleneoxy)]diacetic acid

Three new inorganic–organic coordination polymers based on a “V” shape linking unit 4,4′-[isopropylidenebis( p-phenyleneoxy)]diacetic acid (H 2 L) and Cd II, Zn II and Pb II ions, [Cd( L)(H 2O) 2] n ( 1), [Zn 2( L) 3(H 2O) 6·6H 2O] n ( 2) and [Pb 2Na 2(L) 3(DMF) 4(H 2O) 2·2H 2O] n ( 3), have been prepared and structurally characterized by single-crystal X-ray diffraction analysis. Complex 1 is a 1D zig-zag chain coordination polymer, which is connected by strong hydrogen-bond interactions to result in a 3D network. In complex 2, an infinite 2D (6, 3) network with large hexagonal cavities was created. The whole 2D structure is a noninterpenetrating framework stacked by hydrogen-bonding interactions. Complex 3 is a novel 3D heterometallic coordination polymer, which possesses three different types of isolated channels.