A bi-chain CoII coordination framework bridged by water molecules: magnetic properties and photocatalytic behavior

A new coordination framework, [Co₂(L)₂(bpy)₂(H₂O)]_n (1) (H₂L = (4-phenyl)-2,6-bis(4-carboxyphenyl)pyridine and bpy = 2,2′-bipyridine), has been prepared and structurally characterized. Complex 1 shows an interesting bi-chain substructure bridged by coordinated water molecules, which is further extended into a three-dimensional (3-D) supramolecular structure by π–π stacking interactions. Moreover, the magnetic properties and photocatalytic activity for degradation of methyl orange have been investigated.     

Preparation,structure and photocatalysis of metal-organic frameworks derived from aromatic carboxylate and imidazole-based ligands

Three 3-D metal-organic frameworks (MOFs), [Cd(NDC)(biim-4)]·0.5H₂O (1), [Cd₂(TDC)₂(biim-4)₂(H₂O)₂] (2) and [Zn₂(biim-4)₂(TDC)₂]·2.5H₂O (3) (biim-4 = 1,4-bis(1-imidazolyl) butyric alkyl; H₂NDC = 1,4-naphthalene dicarboxylic acid; H₂TDC = thiophene-2,5-dicarboxylic acid), have been synthesized under hydrothermal conditions and structurally characterized by single X-ray diffraction. The three MOFs have high photocatalytic degradation effects on methyl orange under UV irradiation. Through electronic structure analysis combined with time-dependent density functional theory calculations, catalytic performances of these materials are correlated with the molecular composition and the optoelectronic properties of the samples.     

Assembly of two new polyoxometalate-templated supramolecular compounds by utilizing flexible 1,4-bis(pyrazol-1-ylmethyl)benzene ligand

Two new polyoxometalate-templated supramolecular compounds, [Cu^I₄(bpmb)₄][PMo^VI₁₁Mo^VO₄₀] (1) and [Cu^I₄(bpmb)₄SiW₁₂O₄₀] (2) (bpmb = 1,4-bis(pyrazol-1-ylmethyl)benzene), have been synthesized under hydrothermal conditions and characterized by routine methods. Structural analysis shows that in 1, there exist crown-like [Cu^I₄(bpmb)₄] coordination macrocycles, and the Keggin polyanions [PMo ^VI₁₁Mo^VO₄₀]^4? (abbr. as PMo₁₂), which direct the crown-like macrocycle to form a 3-D supramolecular framework. In 2, there exist unusual meso-helix chains, and these chains are mutually interlaced in a wave–trough pattern, but without intersection resulting in a multi-cavity layer, in which the [SiW₁₂O₄₀]^4? (abbr. as SiW₁₂) clusters as guest molecules occupy the cavities of the layers. The distinct structural features of the two compounds suggest that Keggin polyanions should play a significant role in the process of assembly. Electrocatalytic properties of 1 and 2 were investigated.     

Two inorganic–organic hybrids based on a polyoxometalate: Structures,characterizations, and epoxidation of olefins

Two new inorganic–organic hybrids, [Co₃(bpdo)₆(H₂O)₄Cl₂][SiW₁₂O₄₀]·H₂O (Co-SiW) and [Ni₃(bpdo)₆(H₂O)₄Cl₂][SiW₁₂O₄₀]·H₂O (Ni-SiW) (bpdo = 4,4′-bis(pyridine-N-oxide)), were synthesized from the Keggin-type [SiW₁₂O₄₀] anion and Co(II) and Ni(II) under hydrothermal conditions, respectively, and characterized by elemental analyses, powder XRD, IR spectra, and single-crystal X-ray diffraction. The structural analysis indicates that the 1D chain is constructed from a POM-based half-cage as a secondary building block linked by bridging bpdo ligands. The zigzag chains further stack into a three-dimensional body with channels. The 3D network structure with amphiphilic cavities is shaped by electrostatic interactions through the planes, which has potential to allow molecules such as styrene and H₂O₂ ingress and egress. Both of the hybrids demonstrated catalytic activity for epoxidation of olefins, which was examined using styrene and aqueous hydrogen peroxide (30%) as oxidant in acetonitrile, along with Co-SiW and Ni-SiW in a heterogeneous manner at 60 °C. Moreover, the conversion of epoxidation reaction in a heterogeneous manner is close to that of homogeneous catalysis, while being conveniently recovered and steadily reused without change of catalyst structure after epoxidation reactions.     

Syntheses and electrochemical properties of three supramolecular architectures based on Keggin silicontungstates and different metal-organic units

Three new compounds [Mn(H₂O)₂(bimb)₂(H₃SiW₁₂O₄₀)₂](bimb)₄ (1), [Zn₂(bimb)₄(H₂O)₄][SiW₁₂O₄₀] (2), and [Ni₂(bimb)₄(H₂O)₄][SiW₁₂O₄₀] (3) (bimb = 1,3-bis(1-imidazoly)benzene) have been synthesized under the same hydrothermal reaction except for tuning the metal cations (Mn²⁺, Zn²⁺, and Ni²⁺). Structural characterizations show that the three compounds possess distinct structural motives. Compound 1 displays a supramolecular one-dimensional (1 D) chain formed by π···π interactions that occur among the almost parallel bimb ligands from adjacent [Mn(H₂O)₂(bimb)₂(SiW₁₂O₄₀)₂] dimers. Compound 2 shows a supramolecular two-dimensional (2D) layer achieved by intermolecular (C–H···O) hydrogen bondings between the Zn₂(bimb)₄ molecular loops and the SiW₁₂ anions. Compound 3 also exhibits a supramolecular 2D layer, but it is different from 2, which is generated by the π···π interactions among adjacent 1D polymeric chains. The distinct structural features of the three compounds suggest that the metal cations should play a significant role in the process of assembly. Additionally, the electrochemical properties of compounds 1–3 have been investigated, and the results indicate that compounds 1–3 possess excellent electrocatalytic activity toward reduction of both iodated and nitrite molecules.     

Supramolecular compounds constructed from Keggin anions and metal–organic complex cations of 3-aminopyrazine-2-carboxylic acid

Three new supramolecular compounds based on Keggin-type polyoxometalate (POM) and transition metal complexes, [M(Hapca)₂(H₂O)₂]₂[SiW₁₂O₄₀]·nH₂O, (M = Ni^II(1), Zn^II(2), n = 12; Co^II (3), n = 15; Hapca = 3-aminopyrazine-2-carboxylic acid), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analysis, TG analyses, IR and fluorescence spectroscopy. The X-ray structrual analysis reveals that three compounds are isostructural with a P21/c space group. [M(Hapca)₂(H₂O)₂] ₂ ⁴⁺ are linked together via O···N hydrogen-bonding interaction to give birth to 2D layer with rectangle grids. Anions [SiW₁₂O₄₀]^4? are located in the cavities and link the 2D layers into 3D supramolecular architecture via hydrogen bonds. The compounds represent the first examples of self-assembly of 2D metal–Hapca complex supramolecular “host” networks formed by hydrogen bonding interactions and “guest” polyoxoanion species. In addition, solid-state luminescence properties of compounds 2 and 3 have been studied at room temperature.     

Keggin-Type Polyoxometalate Cluster Functionalized with Dinuclear M-H2biim (M = Cu, Ag) Metal–Organic Segments

Three inorganic–organic hybrid complexes, [Cu₂(H₂biim)₂(OH)₂]₂(SiW₁₂O₄₀)·2H₂O (1), [Cu₂(H₂biim)₂]₂(SiW₁₂O₄₀)·2H₂O (2) and [Ag₂(H₂biim)₂]₂(SiW₁₂O₄₀)·2H₂O (3) (H₂biim = 2, 2′-biimidazole), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, PXRD, TG and single-crystal X-ray diffraction. The crystallographic analysis reveals that in compounds 1–3, the Keggin polyanions [α-SiW₁₂O₄₀]^4? act as inorganic building blocks, which are linked with the dinuclear metal–organic units via Cu–O bonds in compound 1, or through supramolecular interactions in compounds 2 and 3. Compound 1 shows a 3D supramolecular structure constructed by net-like layers. Compounds 2 and 3 display 2D layer structures which were composed of wave-like chains. In addition, these compounds show electrochemical activities, and photoluminescence properties are measured in the solid state.     

Assembly of a Supramolecular Architecture Based on Keggin POMs and Lanthanide Coordination Cations

Two new compounds based on Keggin polyoxometalates (POMs) [SiW₁₂O₄₀]⁴⁻ (SiW₁₂), [Na(H₂O)₃(H₂L)SiW₁₂O₄₀](H₂L)₂   6H₂O (1), and [Ce(H₂O)₃(HL)₂(H₂L)]₂[SiW₁₂O₄₀]₂ 10H₂O (2) (HL = C₆H₅NO₂ = isonicotinic acid), have been conventionally synthesized and characterized by routine methods. Compound 1 possesses a 1D right-handed helical structure constructed by SiW₁₂O₄₀ ⁴⁻ {SiW₁₂} and [Na(H₂O)₃(HL)] complexes. Interestingly, these right-handed helical chains are linked together via H-bonds forming a novel chiral layer. By using the similar synthesis method to that for compound 1, except for employing Ce³⁺ cations in instead of La³⁺ cations, a 3D supramolecular compound 2 based on SiW₁₂ and Ce³⁺ coordination cations has been obtained, which contains 1D channels along a axis. Additionally, the luminescence properties of 2 were studied. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Solvent-controlled structural variation from 1D+2D→3D network with coexistence of polycatenation and polythreading to the 2D→3D polythreaded array

This article represents two types of entanglements, [Co₂(bibp)(BTB)₂][Co(bibp)₂(H₂O)₂] (1) and [Co₃(bibp)₂(H₂O)₂(BTB)₂]·2H₂O·2DMF (2) (bibp = 4,4′-bis(1-imidazolyl)biphenyl and H₃BTB = 1,3,5-tris(4-carboxyphenyl)benzene), which are 2-D→3-D polycatenated frameworks formed by parallel catenation of 1-D+2-D→2-D polythreaded motifs based on the double-layered sheet penetrated by ribbons of rings (1) and a 2-D→3-D mutual polythreading of three double-layered sheets with dangling arms (2), which is assembled by the same initial materials by simply changing the volume ratio of water/DMF medium.     

Syntheses,structures, and fluorescent properties of four Co(II) coordination polymers based on 5-hydroxyisophthalic acid and structurally related bis(benzimidazole) ligands

Four cobalt(II) coordination polymers, {[Co(HO-BDC)(bbp)]}_n (1), {[Co(HO-BDC)(bmbp)₂]·(H₂O)₂}_n (2), {[Co(HO-BDC)(bbb)]}_n (3), and {[Co₂(HO-BDC)₂(bmbb)₂]·(H₂O)₃}_n (4), where HO-H₂BDC?=?5-hydroxyisophthalic acid, bbp = 1,3-bis(benzimidazol-1-yl)propane, bmbp = 1,3-bis(2-methyl-benzimidazol-1-yl)propane, bbb = 1,4-bis(benzimidazol-1-yl)butane, and bmbb = 1,4-bis(2-methyl-benzimidazol-1-yl)butane, have been synthesized and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, thermogravimetric analyses, and fluorescence properties. Compounds 1 and 3 are 4-connected 2-D networks with (4⁴·6²) topology. Compound 2 is a 1-D chain, while 4 features a 1-D ladder. These 1-D and 2-D complexes are further connected by hydrogen bonds to form 3-D supramolecular architectures. Complexes 1–4 showed very strong yellow luminescence emission.     

Two new organic-inorganic hybrid compounds induced by γ-[Mo8O26]4− and [PMo12O40]3−

Two new organic–inorganic hybrid compounds, [Cu^II(btb)_1.5(γ-Mo₈O₂₆)_0.5(H₂O)]·2H₂O (1) and [Cu^II₂(btb)₄(PMo^VMo^VI₁₁O₄₀)]·2H₂O (2) (btb = 4-butyl-1,4-bis(1,2,4-triazole), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, IR spectra and elemental analyses. In 1, there exists a ladder-like metal-organic chain with the bidentate [γ-Mo₈O₂₆]^4? anions inserting into the grids. Adjacent chains share the same Cu-btb lines of the ladder to form a 2-D layer. Compound 2 also has a ladder-like metal-organic chain. The tetradentate [PMo₁₂O₄₀]^3? anions embed in the grids. The same Cu-btb line is shared by adjacent chains to build a 2-D layer. The btb ligands link adjacent layers to form a 3-D framework. Moreover, we also have investigated the electrochemical and photocatalytic properties of 1 and 2.     

Syntheses,structures and photocatalytic degradation of organic dyes for two isostructural copper coordination polymers involving in situ hydroxylation reaction

Two copper(II) coordination polymers, {[Cu₂(btre)(hsuc)Cl(H₂O)]·1.5H₂O}_n (1) and {[Cu₂(btre)(hsuc)Br(H₂O)]·1.5H₂O}_n (2) (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H₃hsuc = 2-hydroxysuccinic acid), were synthesized by the hydrothermal method via in situ hydroxylation reaction with fumarate (fum), btre and CuCl₂/CuBr₂, and characterized by elemental analyses, IR, TG and X-ray diffraction. 1 and 2 are isostructural and show a 4-connected 2-D network based on [Cu₂O] dimers. 1 and 2 show good photocatalytic activity for the degradation of organic dyes methylene blue and methyl orange under UV light irradiation.     

Trigonal (-3) symmetry octahedral lanthanide(III) complexes of zwitterionic tripodal ligands: luminescence and magnetism

Sandwich coordination complexes, [Ln^III(H₃L)₂]X₃?solvents, of Tb(III), Eu(III), Dy(III), Ho(III) and Er(III) were prepared with two new zwitterionic ester-substituted tripodal amine ligands, tris((2-hydroxy-5-n-butyl benzoate)aminoethyl)-amine (H₃L¹) and tris((2-hydroxy-5-methyl benzoate)aminoethyl)-amine (H₃L²). These ligands were synthesised by condensation of the appropriately substituted salicylaldehyde with tris(2-aminoethyl)amine (tren) followed by in situ reduction of the tris-imine to tris-amine. Subsequent 2:1 reaction with lanthanide(III) ions yields [Ln^III(H₃L)₂]X₃?solvents (L = L¹, L²; X = Cl^?, NO₃^?; solvents = MeOH or H₂O). All complexes were characterised by microanalysis, infrared spectroscopy, high resolution mass spectrometry and solid-state photoluminescence measurements. The crystal structures of [Tb^III(H₃L¹)₂]Cl₃·6MeOH, [Dy(H₃L¹)₂]Cl₃·6MeOH, [Eu^III(H₃L¹)₂]Cl₃·6MeOH and [Tb^III(H₃L¹)₂](NO₃)₃ reveal high-crystallographic ?3 symmetry at the O₆-coordinated octahedral lanthanide(III) ions and that the tripodal ligands are bound in zwitterionic form: the protons from the phenolic oxygens have migrated to the amino nitrogens. Photoluminescence measurements indicate various degrees of energy transfer of the ligand chromophore to the lanthanide ions, as both ligand and lanthanide emission features are observed. Despite the high-crystallographic symmetry and the likely small transverse magnetic anisotropy of the complexes, no evidence of slow relaxation of the magnetisation, characteristic of a single-molecule magnet, was observed for [Tb^III(H₃L¹)₂]Cl₃·MeOH·3H₂O, [Dy^III(H₃L¹)₂]Cl₃·6H₂O, [Ho^III(H₃L¹)₂](NO₃)₃·2H₂O, [Er^III(H₃L¹)₂]·H₂O and [Tb^III(H₃L¹)₂](NO₃)₃ down to 2.0 K.     

Two New One-Dimensional Chain-Like Compounds Constructed from the Sandwich-Type Polyoxotungstate Clusters

Two new one-dimensional chain-like compounds, K₄Na₄[Mn₂(H₂O)₈Mn₄(H₂O)₂(GeW₉O₃₄)₂] · 20.5H₂O (1) and K₂Na₄Cu₂(H₂O)₁₂[Cu(H₂O)₂Cu₄(H₂O)₂(SiW₉O₃₄)₂] · 15H₂O (2), constructed from the sandwich-type clusters, have been obtained by the routine synthetic reactions in aqueous solutions, and their structures were determined by X-ray single crystal diffraction analysis. The crystal data is following: for 1, space group, monoclinic, P _21/n, a = 16.693(3) Å, b = 14.935(3) Å, c = 20.090(4) Å, β = 92.23(3)°, V = 5004.7(17) ų, Z = 2; For 2, space group, triclinic, P _?1, a = 11.744(2) Å, b = 13.415(3) Å, c = 17.609(4) Å, α = 73.08(3)°, β = 82.68(3)°, γ = 65.18(3)°, V = 2409.1(8) ų, Z = 1. The crystal structure of 1 shows a 1D ladder-like chain, built up of the sandwich anions [Mn₄(H₂O)₂(GeW₉O₃₄)₂]^12? and the Mn²⁺ ions. Compound 2 is a polymeric chain, composed of the Cu-substituted sandwich-type anions [Cu₄(H₂O)₂(SiW₉O₃₄)₂]^12? linked by the Cu(H₂O)₄ clusters. These extended materials based on the sandwich-type polyoxoanions are rarely reported in the POM chemistry.     

Syntheses and crystal structures of phthalato-, succinato-, maleato-, acetylenedicarboxylato-bridged [bis(2-pyridylcarbonyl)amide]copper(II) complexes

Self-assemblies of the 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and Cu(OH)₂ in the presence of dicarboxylate ligands yielded four new complexes, [Cu₄(bpca)₄(L1)₂(H₂O)₂]·5H₂O (1), [Cu₂(bpca)₂(L2)(H₂O)₂]·2H₂O (2), [Cu₂(bpca)₂(L3)(H₂O)₂]·H₂O (3), and [Cu₂(bpca)₂(L4)(H₂O)₂]·3H₂O (4) (bpca = bis(2-pyridylcarbonyl)amide anion, H₂L1 = phthalic acid, H₂L2 = succinic acid, H₂L3 = maleic acid, H₂L4 = acetylenedicarboxylic acid). Their structures were determined by single-crystal X-ray diffraction analyzes and further characterized by IR spectra and thermogravimetric analyzes. The five-coordinate Cu ions in 1 are bridged by phthalate to form 1-D chains, which are assembled into 3-D frameworks by extensive hydrogen bonds. Compounds 2–4 possess similar structures, built up of [Cu₂(bpca)₂(L)(H₂O)₂] (L = L2 for 2, L3 for 3, L4 for 4) and lattice molecules. The 3-D frameworks of 2–4 are completed by hydrogen bond interactions.     

Dinuclear nickel(II) complexes with Schiff base ligands: syntheses, structures and bio-relevant catalytic activities

Three Ni(II) complexes of cresol-based Schiff-base ligands, namely [Ni₂(L¹)(NCS)₃(H₂O)₂], (1) [Ni₂(L²)(CH₃COO)(NCS)₂(H₂O)] (2) and [Ni₂(L³)(NCS)₃] (3), (where L¹ = 2,6-bis(N-ethylpyrrolidineiminomethyl)-4-methylphenolato, L² = 2,6-bis(N-ethylpiperidineiminomethyl)-4-methylphenolato and L³ = 2,6-bis{N-ethyl-N-(3-hydroxypropyl iminomethyl)}-4-methylphenolato), have been synthesized and structurally characterized by X-ray single-crystal diffraction in addition to routine physicochemical techniques. Density functional theory calculations have been performed to understand the nature of the electronic spectra of the complexes. Complexes 1?C3 when reacted with 4-nitrophenyl phosphate in 50:50 acetonitrile?Cwater medium promote the cleavage of the O?CP bond to form p-nitrophenol and smoothly convert 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ) either in MeOH or in MeCN medium. Phosphatase- and catecholase-like activities were monitored by UV?Cvis spectrophotometry and the Michaelis?CMenten equation was applied to rationalize all the kinetic parameters. Upon treatment with urea, complexes 1 and 2 give rise to [Ni₂(L¹)(NCS)₂(NCO)(H₂O)₂] (1??) and [Ni₂(L²)(CH₃COO)(NCO)(NCS)(H₂O)] (2??) derivatives, respectively, whereas 3 remains unaltered under same reaction conditions.     

Influence of secondary ligand on structures and topologies of lanthanide coordination polymers with 1,3,5-triazine-2,4,6-triamine hexaacetic acid

A series of new lanthanide coordination polymers has been synthesized and structurally characterized; [Ln₄(TTHA)₂(pzac)(H₃O)₂(H₂O)]·5H₂O (Ln = Pr (1a) and Nd (1b)), [Sm₈(TTHA)₄(pzac)_0.5(H₃O)(H₂O)_7.5]·4H₂O (2), [Ln₄(HTTHA)₂(SO₄)(H₂O)₄]·5H₂O (Ln = Pr (3a) and Nd (3b)), where H₆TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid, and H₂pzac = 2,5-dioxo-piperazine-1,4-diacetic acid. The compounds feature 3-D frameworks comprising the deprotonated H₆TTHA as the primary ligand and either the in situ generated pzac^2? or sulfate as the secondary ligands. The influence of the deprotonated H₆TTHA in directing the framework structures through preferential coordination modes and molecular conformation is described. The effect of the secondary ligands in increasing the compactness of the frameworks and in the alternation of the framework topologies based on the four-connected pts type is described.     

Dodecanuclear water cluster in bowl: microwave-assisted synthesis of a heptanuclear cobalt(II) cluster

A heptanuclear double-bowl-like cluster [Co₇(mmp)₆(OH)₆]₂·(ClO₄)₂·12H₂O (1·12H₂O, Hmmp is 2-methoxy-6-methyliminomethyl-phenol) has been synthesized through the microwave-assisted reaction of Co(ClO₄)₂·6H₂O with 2-hydroxy-3-methoxy-benzaldehyde (Hhmb) and methylamine in mixed solvent (acetonitrile : distilled water = 9 : 1) for 29 min. 1·12H₂O was heated until 180 °C and it formed a non-water complex [Co₇(mmp)₆(OH)₆]₂·(ClO₄)₂ (1). The core of 1·12H₂O can be described as a double bowl, while the dodecanuclear water cluster stands on the bowl. Magnetic investigations show that 1·12H₂O and 1 display ferromagnetic interaction between cobalt ions. Moreover, 1 shows single molecular magnet behavior under 2 K. Magnetic studies indicate that hydrogen bond plays a vital role in transferring magnetic exchange effects.     

Subtle difference of [SiMo12O40]4− and [PMo12O40]3− inducing two new distinct Keggin-Ag-(1H-Pyrazole) compounds

Two new inorganic-organic hybrid compounds based on α-Keggin clusters and Ag-(1H-Pyrazole) subunits, [AgL₂]₄[SiMo₁₂O₄₀] (1) and [AgL₂]₃[PMo₁₂O₄₀] (2) (L = pyrazole), have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction. In 1, there are two kinds of chains, the chains linked by two [AgL₂]⁺ clusters and the other linked only by one [AgL₂]⁺, which further connect by sharing [SiMo₁₂O₄₀]^4? anions to construct a 2-D layer. In 2, four-supporting [PMo₁₂O₄₀]^3? anions are fused by [Ag(1)L₂]⁺ subunits to form a 1-D chain. Through weak interactions of Ag?O (3.091 Å) a 2-D supramolecular layer is constructed. Additionally, the electrochemical properties of title compounds and the photocatalytic properties of 2 have been studied.     

Synthesis,Structure, and Properties of Two Supramolecular Compounds Based on Silicotungstic Acid and Transition Metal(II) Coordinated Isonicotinic Acid

Two compounds, namely [Cd(HINA)₂(µ₂‐H₂O)(H₂O)₂]₂[SiW₁₂O₄₀]·6H₂O ( 1 ) and [Co(HINA)₃(H₂O)₃][Co(HINA)₂(H₂O)₄][SiW₁₂O₄₀]·2H₂O ( 2 ), have been synthesized from the aqueous mixture containing H₄SiW₁₂O₄₀, isonicotinic acid (HINA), and M(CH₃COO)₂ (M=Cd and Co). The compounds have been characterized by elemental analysis, IR spectroscopy, TG analysis, and single‐crystal X‐ray diffraction. The dinuclear coordinated cadmium units in compound 1 are linked to form 2D layer parallel to ab plane through π‐π interactions and hydrogen bonds. Compound 2 contains two different types of coordinated metal cations, [Co(HINA)₃(H₂O)₃]²⁺ and [Co(HINA)₂(H₂O)₄]²⁺, which construct 2D layer along bc plane through π‐π interactions and hydrogen bonds. In both compounds, the Keggin anions are located inside the channels and cavities formed from stack of the coordinated metal cations, which further achieve the 3D supramolecular structure through hydrogen bonds. The luminescent property of compounds 1 and 2 has been investigated.