Multicarboxylate Ligands Research Articles

A series of coordination complexes based on unsymmetrical multicarboxylate ligands: syntheses, structures and properties

Six new coordination polymers, namely, [Zn2(L1)2phen2(H2O)2] (1), [M3(L1)2(OH)2 (4,4′-bpy)(H2O)2]·2H2O (M = Cd (2), Co(3)), [Cd5(L1)2(OH)2(trz)4(L3)]·2H2O (4), [Zn(HL2)(4,4′-bpy)] (5) and [Cd3(L2)2(L3)2(H2O)5]·H2O (6) (H2L1 = 4-(1-carboxy-ethoxy)-benzoic acid, H3L2 = 5-(1-carboxy-ethoxy)-isophthalic acid, L3 = 1,2-bis(1,2,4-triazole-1-yl)ethane, phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine, Htrz = 1,2,4-triazole), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 is a molecular square composed by two Zn ions, two L1 and two phen ligands. Compounds 2 and 3 are isostructural and display 3D frameworks constructed by 1D M–O–M chains. Compound 4 exhibits a 3D 8-connected network with hex topology based on the pentanuclear Cd cluster and the point symbol is (36·418·53·6). Compound 5 shows a 2D wavelike layer with sql topology. Compound 6 reveals a 3D three-fold interpenetrating architecture having (3,4)-connected dmd topology with the point symbol of (4·102)2(42·104). These compounds have been characterized by infrared spectroscopy (IR) and thermal gravimetric analyses (TGA). In addition, the photoluminescent behaviour of 1, 2, and 4–6 has been investigated in detail.

Indium metal–organic frameworks as catalysts in solvent-free cyanosilylation reaction

Two new Indium MOFs with the bending multicarboxylate ligand H2dpmda as a linker and different N-donor ancillary ligands were obtained; the two compounds are isoreticular with 2D-hcb uninodal 3-connected nets. Comparison of their activity in cyanosilylation reactions with another eight In-MOFs is also reported. Eight out of the ten resulted in being good catalysts under mild and environmentally friendly conditions. Correlations between indium coordination number (CN), framework topology and catalytic activity are made and discussed, demonstrating that among the studied MOFs, the indium material named InPF-6 with the formula [In2(dpa)3(1,10-phen)2]·H2O is the most effective catalyst. A possible catalytic mechanism is discussed.

Construction of a series of coordination polymers from three imidazole-based multi-carboxylate ligands

2-Carboxylphenyl, 3-carboxylphenyl and 4-carboxylphenyl groups were introduced into the 2-position of imidazole-4,5-dicarboxylate system, respectively, obtaining three multi-functional ligands 2-(2-carboxylphenyl)-1H-imidazole-4,5-dicarboxylic acid (o-CPhH4IDC), 2-(3-carboxylphenyl)-1H-imidazole-4,5-dicarboxylic acid (m-CPhH4IDC) and 2-(4-carboxylphenyl)-1H-imidazole-4,5-dicarboxylic acid (p-CPhH4IDC). Then the three organic ligands are employed to react with Sr(II) and Cd(II) ions. Subsequently, five 3D or 2D polymers, [Sr(o-CPhH2IDC)]n (1), [Sr3(m-CPhHIDC)2(H2O)3]n (2), [Sr(p-CPhH2IDC)(H2O)]n (3), [Cd(o-CPhH2IDC)(H2O)2]n (4) and {[Cd3(m-CPhHIDC)2(H2O)8]·2H2O}n (5), have been hydro(solvo)thermally synthesized and structurally characterized. Compound 1 is a (5,5)-connected 3D structure with unique “H-shape” channels. Three kinds of coordination environments around the Sr atoms are exhibited in compound 2. Both compounds 1 and 2 contain unusual irregular cages. Compound 3 displays a (4,6)-connected 3D porous framework composed of right-handed helices connected by p-CPhH2IDC(2−) anions. Both compounds 4 and 5 present net-like layer structures. These various architectures demonstrate the versatile coordination abilities of the three imidazole-based multi-carboxylate ligands.

Assembly and tunable luminescence of lanthanide-organic frameworks constructed from 4-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylate ligand

A novel N-heterocycle multicarboxylate ligand 4-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4dpda) was synthesized, and then reacted with lanthanide salts to yield a series of lanthanide metal–organic frameworks, [Ln(Hdpda)(H2O)4]·0.5(H2O) (Ln=Eu(1), Gd(2), Tb(3), Dy(4)) and [Tb1−xEux(Hdpda)(H2O)4]·0.5(H2O) (x=0.1–10mol%). Single crystal X-ray diffraction and powder XRD patterns confirm these MOFs are isostructural. Luminescent measurements suggest that the ligand can provide efficient sensitization for the lanthanide ion Tb(III) and Eu(III) in the mixed lanthanide MOFs. Additionally, the luminescence color of the mixed MOFs can be easily tuned from green to green–yellow, yellow, orange, red–orange and red by varying the molar ratio of Eu(III)/Tb(III).

Syntheses, structures, and properties of four coordination compounds constructed from asymmetric semi-rigid V-shaped multicarboxylate ligand

Four new compounds, [Mn(HL)(phen)2(H2O)] (1), [Ni(HL)(phen)2(H2O)] (2), [Zn(HL)(4,4′-bipy)1.5(H2O)] n · 2nH2O (3) and [Zn2(HL)2(H2O)6] (4), have been synthesized from an asymmetric semi-rigid V-shaped multicarboxylate 4-(4-carboxy-phenoxy)-phthalic acid (H3L) with 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy) as auxiliary ligands. Single-crystal X-ray diffraction analysis reveals that 1, 2 and 4 have 0-D structures with 3-D supramolecular frameworks formed by intermolecular hydrogen bonds. Compound 3 shows a 1-D infinite ribbon bridged by 4,4′-bipy, which further forms a 3-D supramolecular architecture by π–π stacking interactions and hydrogen bonds. Thermal stabilities of 1–4 and luminescence properties of 3 and 4 have also been investigated.

Solvothermal synthesis and characterizations of three coordination polymers based on multicarboxylate ligand

Abstract Three novel polymers, [Cd1.5(oba)(pcla)(CH3OH)](1), [Zn (oba)(4,4′-bpy)1.5]4(4,4′-bpy)2(H2O)5 (2) and [Cu2(oba)2(DMF)](DMF)(H2O)(3) (H2oba = 4,4′-oxydibenzoic acid, Hpcla = picolinic acid) have been solvothermally synthesized and structurally characterized. 1 shows 2-D double layer structure with 1-D helix channels, while 2 and 3 display 3-D porous frameworks with different channels in their shapes and sizes. Moreover, complex 3 displays interesting hydrogen sorption behaviors and these materials are expected to afford potential applications.

A Guest‐Dependent Approach to Retain Permanent Pores in Flexible Metal–Organic Frameworks by Cation Exchange

Two anionic metal-organic frameworks were successfully prepared based on pre-designed flexible multicarboxylate ligands and indium cations. Owing to the flexibility of the bridging organic linkers, which could not themselves sustain the frameworks, both of the frameworks showed thermal instability and shrinkage after removal of guest solvent molecules. Inspired by bamboo, we used a guest-dependent approach to tune the permanent porosity of the MOFs. In this approach, several tetraalkyammonium cations of different sizes were introduced into the channels by cation exchange to act as partitions and to support the main frameworks. This approach significantly enhanced the stability of the framework and its permanent porosity. Moreover, the gas-adsorption properties (such as gate sorption, hysteresis, and selectivity) of the MOFs were also modulated by the judicious choice of guest cations.

Zn(II) and Cd(II) metal–organic frameworks (MOFs) constructed from a symmetric triangular semirigid multicarboxylate ligand: Synthesis, structures and luminescent properties

Three transition metal coordination polymers [Zn2(H2L)(2,2′-bpy)2(H2O)]n∙2nH2O (1), [Zn2(H2L)(2,2′-bpy)2]n (2), and [Cd2(H2L)(2,2′- bpy)2(H2O)2]n∙2nH2O (3), have been assembled from a semirigid triangular multicarboxylate ligand 3,3′,3″-(1,3,5-phenylenetri(oxy))triphthalic acid (H6L) with the help of 2,2′-bipyridine (2,2′-bpy) ligand. X-ray single crystal diffraction analysis reveals that complex 1 crystallizes in the space group of Pī and displays a one-dimensional (1D) ladder chain structure constructed from 2,2′-bpy ligand and H2L ligand, which stacks together in an -ABCABC- motif, featuring a mutually embedded chained structure. In complex 2, the H2L ligands bridge the adjacent Zn(II) atoms into a complicated ribbon chain along the b axis. There is π–π stacking interaction between the chains, which results in the formation of a 2D supramolecular structure. Complex 3 also exhibits a 1D ladder-like chain. The different molecular structures for complexes 1 and 2 formed from the same H6L and Zn(NO3)2∙6H2O in different metal-to-ligand ratios in the presence of NaOH, reveals the influence of metal–ligand ratio on the structure of the coordination polymer. In contrast, a series of same reaction using Cd(NO3)2∙4H2O as a starting material instead of Zn(NO3)2∙6H2O only led to the formation of 3, illustrating the fact organic ligands display different coordination preferences at different metal ions. In addition, the thermal and luminescent properties of complexes 1–3 were also investigated.

Synthesis, Spectral Properties of Tb (III) Complexes with 2，2'-Dithiosalicylic Acid

A new terbium complex with aromatic multicarboxylate ligand, 2, 2'-dithiosalicylic acid (L), has been synthesized. The terbium complex was characterized by elemental analysis, infrared spectrum and luminescent spectra, and the complex conforms to 1:1 metal-to-ligand stoichiometry. The complex is stable in air. The results show that the Tb (III) ion in the complex is coordinated by oxygen atoms of the ligand and the oxygen atoms of the nitrate and coordinated water molecules. The luminescent properties of terbium complex have also been investigated in solid state and in organic solvents.

Structure and physical properties of Mn(II) and Co(II) complexes with multicarboxylate ligands

Three new metal-organic coordination polymers, [Mn(4,4′-bpy)(H2BTCA)(H2O)2](4,4′-bpy) (1), [Na2Co(BTCA)0.5(OXA)]·3H2O (2) and [Na2Co(BTCA)(H2O)2] (3), (H4BTCA = benzene-1,2,4,5-tetracarboxylic acid, H2OXA = oxalic acid) have been synthesized, which are characterized by elemental analysis, infrared spectrum and x-ray crystal diffraction. Complex 1 possesses a 3D polymeric structure, which is comprised of (4,4)-layers. Hydrogen bonds play a dominant role in the construction of the final 3D supramolecule. 1D channels are observed in complex 2, which can be ascribed to pillared-layer motifs.

Synthesis, crystal structures, and luminescent properties of Cd(ii) coordination polymers assembled from asymmetric semi-rigid V-shaped multicarboxylate ligands

A series of seven Cd(II) coordination polymers, namely [Cd3(L1)2(phen)3]n·(H2O)2n (1), [Cd3(L1)2(2,2′-bpy)3(H2O)2]n·(H2O)3n (2), [Cd3(L1)2(4,4′-bpy)2]n·(H2O)4n (3), [Cd3(L2)2(phen)2]n (4), [Cd3(L2)2(2,2′-bpy)2]n (5), [Cd3(L3)2(phen)2(H2O)]n·(H2O)2n (6), and [Cd3(L4)2(phen)2(H2O)2]n·(H2O)3n (7), have been prepared on the basis of four asymmetric semi-rigid V-shaped multicarboxylate ligands including 4-(2-carboxyphenoxy)phthalic acid (H3L1), 3-(2-carboxyphenoxy)phthalic acid (H3L2), 3-(4-carboxyphenoxy)phthalic acid (H3L3), and 4-(4-carboxyphenoxy)phthalic acid (H3L4) with the help of 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bpy), or 4,4′-bipyridine (4,4′-bpy) as secondary ligand. Single-crystal X-ray diffraction analysis reveals that compounds 1, 4, 5, and 6 exhibit one-dimensional (1D) double chain structures constructed from trinuclear Cd(II) clusters, which further forms 2D supramolecular architecture via intermolecular π–π interaction. Complex 2 possesses a 3D supramolecular network assembled from 2D layered architecture composed of dinucelar cadmium subunits and isolated Cd(II) ions via intermolecular π–π interaction. Compound 3 shows a 3D framework structure which is generated from 2D layered motif comprised of trinuclear cadmium subunits pillared by 4,4′-bpy ligands, while the 3D framework of 7 is constructed from two different directional ribbon chains consisting of dinuclear cadmium clusters and isolated Cd(II) ions as node. The different molecular structure for compounds 1–3 formed from the same L1 ligand reveals the spacer effect of secondary ligands on tuning the structure of coordination polymers, while the structural difference among 1, 4, 6, and 7 built from different asymmetric semi-rigid V-shaped multicarboxylate ligand (L1, L2, L3, or L4) but employing the same secondary ligand of phen reveals the important role of the positions of carboxylic substituents at the asymmetric multicarboxylate ligand in the formation of coordination compounds. Photophysical properties over the series of complexes 1–7 have been systematically and comparatively investigated.

Solvothermal synthesis, structures and physical properties of four new complexes constructed from multi-variant tricarboxylate ligand and pyridyl-based ligands

Solvothermal reactions of partially or wholly deprotonated biphenyl-3,4′,5-tricarboxylate (H3L) with nitrates of cadmium, manganese and cobalt, in the presence or absence of auxiliary 4,4′-bipyridine (bipy) and 1-(3,5-di(1H-imidazol-1-yl)phenyl)-1H-imidazole (timp) ligands in H2O–DMF, produce four new complexes, namely, {[Cd3(L)2(H2O)9]·(H2O)5}n (1), {[Cd2(HL)2(timp)(H2O)4]·(H2O)4}n (2), {Mn(HL)(bipy)0.5(H2O)}n (3), {Co(HL)(bipy)0.5(H2O)}n (4). Their structures have been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra, and thermogravimetric analysis. Complex 1 possesses a three-dimensional (3D) framework composed of two-dimensional (2D) T-shaped molecular bilayer motifs polycatenated with each other. In complex 2, multicarboxylate ligands and timp ligands link Cd centers to generate one-dimensional (1D) ladder structures which are further connected by π–π interactions to form a 3D supramolecular structure. Complexes 3 and 4 are isostructural and possess 2D networks. Magnetic susceptibility measurements indicate that complexes 3 and 4 exhibit ferromagnetic coupling between adjacent Mn(II) ions and Co(II) ions. The photoluminescent properties of 1 and 2 have been studied in the solid state at room temperature.

Syntheses, structures, magnetic and photoluminescence properties of metal–organic frameworks based on aromatic polycarboxylate acids

Six new coordination compounds, namely [Co(H2bptc)]n (1), [Mn(H2bptc)]n (2), [Cd2(bptc)(phen)2(H2O)2]n (3), [Eu2(cpa)3(DMF)2]n (4), [Nd2(cpa)3(DMF)2]n (5) and [Pr2(cpa)3(DMF)2]n (6) (bptc4− = biphenyl-2,2′,4,4′-tetracarboxylate anion, phen=1,10-phenanthroline, cpa2− = 4-chloroisophthalic acid anion) were synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra, and thermogravimetric analysis. Co and Mn compounds are isostructural, and possess a three-dimensional 5, 5-connected network. In Cd compound, multicarboxylate ligand H4bptc link Cd centers to generate a two-dimensional 4, 4-c net structure with phen acting as terminal ligand. Eu, Nd, and Pr compounds have similar structures, and cpa2− ligands link lanthanide cations to generate a two-dimensional sheet structure. Magnetic susceptibility measurements indicate that the Co compound has a dominating ferromagnetic coupling between Co(II) ions, and Mn compound exhibits antiferromagnetic coupling between Mn(II) ions. Furthermore, their luminescent properties are also determined in the solid state at room temperature.

ChemInform Abstract: Indium(III)‐Organic Coordination Polymers with Versatile Topological Structures Based on Multicarboxylate Ligands

AbstractReview: 76 refs.

Secondary ligand-directed assembly of Zn II and Cd II coordination architectures: From 1D to 3D compounds based on pyridine carboxylate ligands

To investigate the influence of spatial extended direction on the resulting structure, three new compounds have been synthesized by the reactions of Zn II or Cd II salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL 1) or 3,4-bis(pyridin-4-ylmethoxy)benzoic acid (HL 2) with two rationally selected multicarboxylate ligands. Without a secondary ligand, an 1D ribbon structure [Zn(L 1) 2]·H 2O ( 1) furnished, the hydrogen bonds extended the structure to a 2D layer. Employing 4,4′-biphenyldicarboxylic acid (H 2bpdc), a 2D layer structure [Zn(L 1)(bpdc) 0.5] ( 2) resulted. The use of 1,3,5-benzenetricarboxylic acid (H 3btc) led to a 3D compound [Cd 2(L 2)(btc)(H 2O)] ( 3). It can be observed from the architectures of 1– 3 that secondary ligands had great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds.

Zn(II) metal-organic frameworks (MOFs) assembled from semirigid multicarboxylate ligands: Synthesis, crystal structures, and luminescent properties

Two new coordination polymers [Zn 2L(2,2′-bpy)] n ∙(H 2O) 2 n ( 1) and [Zn 2L(phen)] n ∙(H 2O) 2 n ( 2) have been assembled from a semirigid multicarboxylate ligand 3,3′-(1,3-phenylenebis(oxy))diphthalic acid (H 4L) with the help of 2,2′-bipyridine (2,2′-bpy) or 1,10-phenanthroline (phen) as secondary ligand. Single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the space group C2/ c and displays a one-dimensional (1D) chain structure constructed from 2,2′-bpy and L ligand, which further forms a two-dimensional (2D) plane via intermolecular π–π interactions. Compound 2 belongs to the space group P 1 ¯ and features a 1D Δ- and Λ-typed chiral chain configuration despite the racemic nature for the whole complex. The neighboring chains with the same chirality are further stacked into a 2D ΔΔΔ- or ΛΛΛ-typed supramolecular structure via intermolecular π–π interactions because of the chiral recognition mechanism. Photophysical properties over complexes 1 and 2 have been comparatively investigated, revealing the effect of secondary ligand on the luminescent properties of these two complexes.

Synthesis, Structures, and Properties of Zinc(II) and Cadmium(II) Complexes with 1,2,4,5-Tetrakis(imidazol-1-ylmethyl)benzene and Multicarboxylate Ligands

Five new coordination polymers, namely, [Cd(L)0.5(HBTC)]·0.2H2O (1), [Cd3(L)2(BTA)2(H2O)2]·H2O (2), [Cd2(L)0.5(BTEC)]·H2O (3), [Zn3(L)(BTC)2(H2O)2]·3H2O (4), and [Zn2(μ2-OH)(L)0.5(BTA)]·H2O (5) were synthesized under hydrothermal conditions by reactions of corresponding Cd(II) or Zn(II) salts with the mixed multidentate ligands of 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L) and 1,3,5-benzenetricarboxylic acid (H3BTC), 1,3,5-benzenetriacetic acid (H3BTA), 1,2,4,5-benzenetetracarboxylic acid (H4BTEC), respectively. The complexes were characterized by single crystal X-ray diffraction, IR, and thermogravimetric and elemental analyses. The Cd(II) complex 1 is a two-dimensional (2D) network with infinite one-dimensional (1D) Cd-HBTC2− chains linked together by L ligands, while the Zn(II) complex 4 with the same mixed ligands has a three-dimensional (3D) structure. The Cd(II) complex with BTA3− and L ligands (2) features an unusual 3D framework, and the Zn(II) complex 5 shows a 3D structure with (63)2(42,84...

A Luminescent Eight-Coordinated 2D Cd(II) Framework Material with Flexible Multi-Carboxylate Ligand

A new coordination polymer of Cd(II), viz., [Cd(ODPA) 2CH 3 CH 2 OH2H 2 O] n (H 4 ODPA = 2,2′,3,3′-oxydiphthalic acid) (1), has been synthesized and structurally characterized by X-ray diffraction. The structure determination reveals that 1 has a 2D network, where each Cd(II) exhibits tetragonal antiprism (uncommon eight-coordinated mode) composed by four bisdentate-chelating carboxylic groups of different ODPA ligands. Moreover, three types of metal-ODPA helices give a 2D herringbone structural motif. The 2D framework stacked in a staggered manner through the – and hydrogen-bonded interactions to form a 3D porous supramolecular structure. Luminescent property for 1 is also discussed.

Metal–organic coordination polymers based on a flexible tetrahydrofuran-2,3,4,5-tetracarboxylate ligand: syntheses, crystal structures, and magnetic/photoluminescent properties

The coordination possibilities of flexible heteroalicyclic ligands with transition metals have been explored. Five CuII, MnII, and CdII coordination polymers with the fully deprotonated tetrahydrofuran-2,3,4,5-tetracarboxylate (L) ligand were synthesized and characterized, sometimes incorporating different auxiliary ligands: {[Cu2(L)(H2O)](H2O)1.42}∞ (1), {[Cu2(L)(2bpy)(H2O)2](H2O)2}∞ (2), {[Cu2(L)(phen)(H2O)2](H2O)1.5(CH3OH)0.25}∞ (3), {[Mn2(L)(phen)2(H2O)](H2O)2}∞ (4), and {[Cd2(L)(phen)2(H2O)](H2O)2}∞ (5) (2bpy = 2,2′-bipyridine and phen = 1,10-phenanthroline). The structural analysis related to 1–5 reveals that the fully deprotonated L ligand displays versatile coordination modes, which result in the generation of a fairly complicated three dimensional (3D) framework for 1 with a Schlafli symbol of (43·67)(46·64), two isostructural two dimensional (2D) puckered layers for 2 and 3 with the decorated binodal (3,5)-connected (3·52)2(32·53·64·7) topology, and two isostructural one dimensional (1D) ribbon-like chains for 4 and 5, respectively. The present work indicates that, in comparison with the rigid aromatic multicarboxylate ligands, tetrahydrofuran-2,3,4,5-tetracarboxylate (L), a heteroalicyclic multicarboxylate ligand, has richer coordination modes and a more flexible ring skeleton, which may remain largely unexpected in the process of constructing metal–organic frameworks (MOFs) and make it more difficult to predict and control the final coordination polymers. Magnetic susceptibility measurements demonstrate that complexes 1 and 4 exhibit antiferromagnetic coupling, whereas 2 and 3 show ferromagnetic coupling, with the corresponding J values of −23.62 cm−1 for 1, 5.18 cm−1 for 2, 3.90 cm−1 for 3, and −0.79 cm−1 for 4. Moreover, complex 5 displays solid blue emission originating from an intraligand π → π* transition of the auxiliary phen ligand.

Diverse Ni(ii) MOFs constructed from asymmetric semi-rigid V-shaped multicarboxylate ligands: structures and magnetic properties

Novel nickel(II) coordination polymers have been constructed from asymmetric semi-rigid V-shaped multicarboxylate ligands with the help of 4,4′-bipyridine (4,4′-bpy) ligand. The hydrothermal reaction between 3-(4-carboxy-phenoxy)-phthalic acid (H3L1) and Ni(OAc)2·4H2O led to the formation of [Ni3(L1)2(μ-4,4′-bpy)3(H2O)2]n·(4,4′-bpy)n·(H2O)5n (1). In contrast, the same reaction using 3-(2-carboxy-phenoxy)-phthalic acid (H3L2) as a starting material instead of H3L1 resulted in [Ni3(L2)2(H2O)4(μ-4,4′-bpy)3]n·(H2O)2n (2) and [Ni3(L2)2(H2O)4(μ-4,4′-bpy)4]n·(H2O)2n (3) at 120 and 150 °C, respectively, revealing the effect of reaction temperature on the structure of the coordination polymer formed from the semi-rigid V-shaped ligand of L2. Single-crystal X-ray diffraction analysis reveals that complex 1 shows a 3D framework structure assembled from right- and left-handed helices together with isolated tubes. This compound represents the first metal–organic hybrid tube constructed from an asymmetric semi-rigid V-shaped multicarboxylate ligand. Compound 2 also exhibits a 3D network composed of discontiguous trinuclear Ni(II) clusters, while the 3D architecture of 3 consisting of isolated Ni(II) ions separated in a long distance is constructed by two kinds of 2D (6,3) networks. Magnetic studies reveal the overall antiferromagnetic interaction between the neighbouring Ni(II) ions in 1–3.