Four New Metal–Organic Supramolecular Networks Based on Aromatic Acid and Flexible Bis(imidazole) Ligand: Synthesis,Structures and Luminescent Properties

Four new metal–organic supramolecular networks, namely, [Zn(H₂pdc)₂(H₂O)₂]·2H₂O·bbi (1), {[Cd(Hpdc)₂]·2H₂O₂·H₂bbi}_n (2), [Zn(BA)₂(bbi)]_n (3), and {[Cd(BA)₂(bbi)]·H₂O}_n (4) (H₃pdc = 3,5-pyrazoledicarboxylic acid, HBA = 3-hydroxybenzoic acid and bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analyses, and single-crystal X-ray diffraction analyses. Compound 1 possesses zero-dimensional (0D) structure, which is finally extended into a two-dimensional (2D) supramolecular network via O–H···O and C–H···O hydrogen bonds. Complex 2 displays a 2D network structure built from Cd²⁺ atoms interconnected by Hpdc^2? ligands. The adjacent networks are further assembled into three-dimensional (3D) supramolecular structure through O–H···O hydrogen bonds. Compounds 3 and 4 show similar one-dimensional (1D) chains, in which four-coordinated Zn(II) atoms and six-coordinated Cd(II) atoms are bridged by bbi ligands. Through O–H···O and C-H···O hydrogen bonding interactions, the 1D chains are further packed into 2D and 3D supramolecular frameworks for 3 and 4, respectively. Obviously, the structural differences among compelxes 1–4 are attributed to the different central metal atoms and organic ligands. In addition, compounds 1–4 exhibit blue fluorescent emission in the solid state at room temperature.     

Two Lanthanide-Based Metal–Organic Frameworks with Flexible Alicyclic Carboxylate Ligands: Synthesis, Crystal Structures, and Near-Infrared Luminescence Property

Two lanthanide-based metal–organic frameworks with flexible alicyclic carboxylate ligands, generally formulated as [Sm(TMG)(HTMG)(H₂O)] (1) and [Nd₂(CHDC)₃(H₂O)] (2), have been successfully synthesized and characterized. They represent the first example of lanthanide-TMG and lanthanide-CHDC systems. Their structures range from 1D infinite chains to 2D extended layer structure. Complexes 2 exhibit strong fluorescent emissions in the near-infrared region at room temperature. Interestingly, the structural difference between compounds 1 and 2 indicates the pH values have subtle influence on the coordination modes of ligands and dimension of LMOFs.     

Syntheses and Crystal Structures of Two Inorganic–Organic Hybrid Frameworks Constructed from Pyridine-2,5-Dicarboxylic Acid

Two novel inorganic–organic hybrid frameworks of [Co(2,5-pydc)(4,4′-bipyo)_0.5(H₂O)₃ · 3H₂O] _n (1) and [Cu_1.5Gd(2,5-pydc)₃(2,2′-bipyo)(H₂O)₄ · 2H₂O] _n (2) (2,5-pydc = pyridine-2,5-dicarboxylic acid; 4,4′-bipyo = 4,4′-bipyridine-N,N′-dioxide; 2,2′-bipyo = 2,2′-bipyridine-N,N′-dioxide) were prepared. Both compounds have been characterized by the elemental analyses, IR spectra, TG analysis and the single crystal diffraction. The salient structural feature for both compounds 1 and 2 is that the 1D chain and the mononuclear fragment are connected by strong hydrogen bond interactions to form 2D structure.     

Construction of Two New Metal–Organic Entangled Frameworks Via Varying Flexible Bis(Imidazole)-based Auxiliary Ligands

Two new metal–organic entangled frameworks, namely [Cd(FA)_0.5(bix)_1.5(H₂O)] _n ·nNO₃ (1) and [Cd(FA)(bib)(H₂O)₂] _n (2) (FA = fumaric acid, bix = 4,4′-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazolyl)butane), have been successfully hydrothermally synthesized through mixed ligands strategy. Single crystal X-ray diffraction analysis reveal that 1 is a 2D → 3D polycatenated framework, while 2 is a triply interpenetrated 4-connected dia topological net. Moreover, both compounds exhibit intense luminescence emission at room temperature.     

Synthesis and Structures of Two Ba(II) Metal–Organic Frameworks Based on Pyridine-2,6-Dicarboxylic Acid N-Oxide

Hydrothermal and solution reactions of pyridine-2,6-dicarboxylic acid N-oxide (2,6-PDCO) and BaCl₂·2H₂O yield two metal–organic frameworks; namely [Ba(2,6-PDCO)] _n (1) and [Ba(2,6-PDCO)·H₂O] _n (2), respectively. Single-crystal X-ray analyses reveal that compound 1 is a dense framework whereas compound 2 is a porous one, though both compounds have an infinite two-dimensional (2D) layer structure. Compounds 1 and 2 are the first examples of pyridine dicarboxylic acid N-oxide introduced into the alkaline earth metal–organic framework.     

Hydrothermal Synthesis of Metal–Organic Coordination Polymers Constructed from Asymmetric Semi-rigid V-shaped Dicarboxylate and Nitrogen-Contained Mixed Ligands

Three new coordination polymers, [Ni(2,4′-oba)(1,10-phen)] _n (1), {[Ni (2,4′-Hoba)₂(4,4′-bipy)(H₂O)₂]·2H₂O} _n (2) and [Zn(2,4′-oba) (4,4′-bipy)] _n (3) (2,4′-H₂oba = 2-(4-carboxyphenoxy)benzoic acid, 1,10- phen = 1,10-phenanthroline, and 4,4′-bipy = 4,4′-bipyridine) have been obtained by hydrothermal synthesis. The framework structures of these polymeric complexes have been determined by single-crystal X-ray diffraction studies. Complex 1 exhibits double-helical chains formed by π–π stacking interactions from the phenyl rings of the 1,10-phen ligands. Complex 2 forms a two-dimensional supramolecular architecture directed by hydrogen bonding. Complex 3 exhibits a three-dimensional structure; Schl?fli symbol of {4⁴·6¹⁰·8}. The luminescent property of compound 3 is discussed.     

Ionothermal Syntheses and Crystal Structures of Two 1D Inorganic–Organic Hybrid Frameworks

Two 1D inorganic–organic hybrid frameworks, namely, [Zn(5-NO₂-bdc)(MIM)₃·H₂O]_n(1) and [Cd(MIM)₂Br₂]_n(2) (5-NO₂-bdcH₂ = 5-nitro-1,3-benzenedicarboxylic acid, MIM = N-methyl imidazole) were synthesized via ionothermal reactions with ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent and template. Both compounds have been characterized by elemental analyses, spectroscopic analyses, thermogravimetric analysis (TGA) and the single crystal diffraction. The zinc(II) center in compound 1 is a slightly distorted five-coordinate trigonal bipyramid, 5-NO₂-bdc²⁻ anions and MIM moieties effectively bridge Zn centers to result in 1D zigzag chains. While Cd(II) center in compound 2 is in an octahedral coordination environment, and two μ²-bridge bromine link two [Cd(MIM)₂] moieties to form a 1D chain structure. In addition, complex 2 exhibits strong fluorescent emission in the solid state at room temperature.     

Structures and Properties of New Cadmium(II) and Copper(II) Metal–Organic Frameworks Based on Flexible Bridged 1,4-bi(1H-imidazol-1-yl)butane Ligand

Two new metal–organic frameworks (MOFs) based on cadmium(II) ions, 1,2-benzenedicarboxylic acid (BDC), flexible ligand 1,4-bi(1H-imidazol-1-yl)butane (BIIM), coordinated water molecules, [(BIIM)(BDC)(H₂O)Cd]_3n (1) and copper(II) ions, BIIM, coordinated water, free thiophene-2,5-dicarboxylate (TDC), free water, {[(BIIM)₄(H₂O)₄Cu₂]·(TDC)₂·(H₂O)₁₂}_n (2) are prepared and characterized by X-ray diffraction, thermal gravimetric analysis (TGA), infrared (IR) spectrum and the photoluminescence property for complex (1). The X-ray diffraction analysis reveals that the structures of complexes 1 and 2 are 2D structures through the C–H···π stacking interactions (for 1) and the BIIM bridging connections (for 2). The IR spectrum for 1 and 2 are presented in the paper, for 1, the strong peaks at 1399 and 1573 cm^?1 are owing to the carboxylic CO₂ ^? symmetry and asymmetry stretching vibrations of BDC. The features of the IR spectrum are consistent with the single crystal structures. The TGA reveal the water is the first lost material from complex, then the ligands removed, and finally the residues of these two complexes are the metal oxide.     

A Flexible Hexacarboxylate-Samarium(III) Metal–Organic Framework: Synthesis, Structure and Spectroscopic Properties

A new flexible triazine-based polycarboxylate metal–organic framework, [Sm₂(TTHA)(H₂O)₄]·9H₂O (I) (TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetate), has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis and FT-IR spectroscopy. Crystal data for I are monoclinic C2/c, a = 12.6974(13) Å, b = 16.7309(12) Å, c = 14.8076(15) Å, β = 91.452(8)°, V = 3,144.7(5) Å³. Each Sm^III ion is 9-coordinate in a distorted tri-capped trigonal prismatic geometry; but, the principal inorganic building block is {Sm₂O₁₆}, which comprises two of these polyhedra that share an edge. The complex exhibits a three-dimensional open-framework structure of approximately 31 % void volume, which comprises two types of channels oriented in three directions; [0 0 1], [1 1 0] and [?1 1 0]. The network can be simplified into either the cooperite (pts) or anatase (ant) topologies depending on the choice of nodes. The UV–Vis spectra of the compound are dominated by the absorption of the TTHA ligand. Thermogravimetric analysis shows that the loss of channel and coordinated water upon heating occurs in two distinct steps.     

Syntheses, Structures and Properties of Two Metal–Iodide Polymers Based on a Flexile N-Donor Ligand

Two novel metal–organic frameworks based on 1,3-bis(imidazol-1-ylmethyl)-benzene (m-bix), namely [(Cu₄I₄)(bix)₂] _n (1) and [HgI₂(bix)] _n (2) have been synthesized and characterized by IR, elemental analysis, thermogravimetry, luminescent properties and X-ray crystallography. The structure of compound 1 exhibits a 1D metal–organic chain composed of Cu₄I₄ clusters and m-bix ligands, and such chains are further united together to generate a 3D supramolecular structure through inter-chain π···π interactions. In compound 2, the HgI₂-bix chains interact each other to form a layer structure through π···π interactions, then the layers are extended to 3D supramolecular architecture through intermolecular C–H···π interactions.     

Synthesis and Hydrogen Storage Properties of Palladium Nanoparticle–Organic Frameworks

We report a simple synthesis of aggregates of individual Pd colloidal nanoparticles linked by bridging ligands that may be used to advance the strong hydrogen storage properties of palladium nanoparticles. The aggregates were characterized by transmission electron microscopy and infrared spectroscopy. The bridged aggregates showed up to 1.0 wt% hydrogen absorption, about 6.7 times that of pristine isocyanide-protected Pd nanoparticles.     

Construction of Two New Metal–Organic Frameworks from Pamoic Acid and N-Containing Auxiliary Ligands

Two new metal–organic frameworks; namely, [Cd₂(pam)₂(bpe)_1.5(DMF)₂(H₂O)] _n ·2n(DMF) (1) and [Cd(pam)(bix)] _n (2) (H₂pam = pamoic acid, bpe = 1,2-di(4-pyridyl)ethylene, bix = 4,4′-bis(imidazol-1-ylmethyl)benzene, DMF = N,N′-dimethylformamide), were solvothermally synthesized via varying the auxiliary ligand. Single crystal X-ray diffraction analysis reveals that compound 1 shows a 2D→3D polythreaded motif based on (3,4)-connected 2D sheets, while compound 2 features a 4-connected sql tetragonal plane net, which further extended into a 3D supramolecular framework through intermolecular CH···π interactions. In addition, the luminescent and thermal stabilities properties of these two compounds were investigated.     

Hydrothermal Synthesis,Crystal Structure and Electrochemical Property of Two Inorganic–Organic Hybrid Frameworks via Hydrogen Bonding

Two inorganic–organic hybrid frameworks, namely [Cu₂(pdca)₂(bibp)(H₂O)₂]·H₂O (1) and [Fe(pdca)(pyco)(H₂O)]·H₂O (2) (H₂pdca = pyridine-2,6-dicarboxylic acid, bibp = 4,4′-bisimidazolylbiphenyl, pyco = picolinate N-oxide) were synthesized via hydrothermal reactions. Both compounds have been characterized by elemental analysis, spectroscopic analysis, thermogravimetric analysis (TGA) and the single crystal diffraction. Complex 1 is dinuclear and five-coordinated copper(II) complex, while complex 2 displays mono-nuclear and six-coordinated iron(III) complex. In the crystal structures of both complexes, the coordinated and crystalline water molecules and H₂pdca ligands contribute to the formation of O–H···O and C–H···O hydrogen bonds, which link the molecules into layers parallel. Cyclic voltammetry (CV) analysis shows one reversible reduction potential at 0.14 V (E_pc) in complex 1, whereas in complex 2 shows a reduction potential at 0.15 V (E_pc) in the cathodic region.     

Targeted Highly-Thermostable Metal–Organic Frameworks Directed by Imidazole: Syntheses, Structures, Thermal Behaviors and Luminescent Properties

Three new isostructural 3D lanthanide MOFs (Ln(HBPTC)(H₂O)) (Ln = Tb (1), Pr (2), Nd (3); H₄BPTC = 3,3′,4,4′-biphenyltetracarboxylic acid) have been synthesized under hydrothermal conditions using imidazole as a structure-directing agent, and characterized by elemental analyses, IR, thermogravimetric analyses (TGA) and powder X-ray diffraction (PXRD) analyses. Topologically, compounds 1–3 demonstrate an intriguing 3D (6, 6)-connected network with the Schläfli symbol of (4¹⁰·6⁵)(4⁹·6⁶); and if the dinuclear (Ln₂) clusters are considered as the single 8-connected nodes, they can be described as a scarcely reported (4, 8)-connected alb net constructed from two intertwining sqp-4 nets. TGA and PXRD analyses reveal that compounds 1–3 exhibit high thermal stability, at least being stable up to 410 °C. Furthermore, the luminescence studies were performed on compound 1 and its dehydrated phase in the solid state at room temperature. The results demonstrate that compound 1 displays intense green emission, implying its potential application as fluorescence material. And the luminescence of 1 is quenched when removing the coordinated water molecules.     

Three New Metal–Organic Polymers Based on Flexible 3-(4-(Carboxymethoxy) Phenyl) Propanoic Acid: Crystal Structures, Luminescent and Magnetic Properties

Three new metal–organic coordination complexes, [Zn₂L(bpp)₂Cl₂] _n (1), [ZnL(bipy)] _n (2), [NiL(bipy)(H₂O)] _n (3), have been synthesized through hydrothermal reactions of flexible 3-(4-(carboxymethoxy)phenyl) propanoic acid(H₂L) with different pyridyl-containing 1,3-bis(4-pyridyl)propane(bpp) or 4,4′-bipyridine(bipy) ligand, and they are characterized by elemetal analysis and single-crystal X-ray diffraction techniques. Complex 1 has a 2-D layer supramolecular network composed of 1-D distorted trapezoidal chains via C–H···π stacking interactions. Complex 2 displays a 2-D lattice-shaped layer structure. Complex 3 has three kinds of O–H···O intermolecular hydrogen bonds, exhibiting a 3-D supramolecular framework. The luminescent properties of complex 1 and 2 have indicated the mixture characteristic of intraligand and ligand-to-ligand charge transition. The magnetic property of 3 has shown the ferromagnetic coupling between Ni²⁺ ions.     

Metal–Organic Framework Based on Pyridine-2,3-Dicarboxylate and a Flexible Bis-imidazole Ligand: Synthesis, Structure, and Photoluminescence

A novel metal–organic framework {[Zn(2,3-pydc)(bbi)]·0.5CH₃CN·2H₂O} _n (2,3-pydc = pyridine-2,3-dicarboxylate, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (1), was prepared under hydrothermal conditions and characterized by elemental analyses, IR and X-ray diffraction. Crystal data for 1 are monoclinic, space group C2/c, a = 19.685(2) Å, b = 14.332(1) Å, c = 16.930(2) Å, β = 121.205(2)°, U = 4085.3(6) Å³, Z = 4. The results reveal that the Zn(II)-atom is five-coordinated with two O-atoms and three N-atoms forming a distorted trigonal bipyramidal geometry. The Zn(II) atoms are bridged by 2,3-pydc and bbi ligands, leading to a three-dimensional network. The Zn···Zn separations are 8.277 Å [through the 2,3-pydc bridge] and 12.638 Å [through the bbi bridge]. Additionally, 1 shows strong fluorescence in the solid state at room temperature.     

Synthesis, Crystal Structure and Properties of a New 3D Supramolecular Metal–Organic Framework with Stable Tunnels

A flexible polycarboxyl ligand of tetrahydrofuran-2,3,4,5-tetracarboxylic acid (H₄THFTCA) and a common rigid aromatic ligand of 1,10-phenanthroline (phen) have been successfully co-assembled with Cu(NO₃)₂·3H₂O to give out a novel 3D supramolecular metal–organic framework (MOF) compound, [Cu₂(THFTCA)(phen)(H₂O)₂·CH₃CH₂OH·3H₂O] _n (1), by a solution self-assembly process. Compound 1 has been characterized as a 2D layered coordination polymer constructed by THFTCA^4? and Cu²⁺ ions, and the layer present a novel (3.5²)(3².5³.6⁴.7) topological network. Interestingly, the layers are fused each other via strong π–π stacking interactions among adjacent ligands of the terminal phen, so that a 3D supramolecular MOF with 1D rhomboidal tunnels array is formed. The thermogravimetric analysis and corresponding powder X-ray diffraction analysis have revealed that the tunnels structure of 1 could be retained after all guest molecules are removed, and the framework could resist the collapse even heating up to 210?°C. An opinion has also been proposed that the larger accessible volume of the guests means the larger stress on the backbone of the MOF after the guests are removed, and the stress is harmful to the stability of the supramolecular porous structure. Finally, the application properties based on the porous structure have also been primarily evaluated.     

Synthesis and Characterization of New Metal–Organic Frameworks Based on Tetracyanoplatinate(II) and N,N′-bis(2-hydroxyethyl)ethylenediamine: Single Crystal Structures of ZnII and CdII Complexes Along with Magnetic Properties of NiII and CuII Complexes

Characterization and synthesis of novel cyano bridged coordination compounds [Ni(bishydeten)Pt(CN)₄] (1), [Cu(bishydeten)Pt(CN)₄] (2), [Zn(bishydeten)Pt(CN)₄] (3), [Cd(bishydeten)Pt(CN)₄] (4) [bishydeten = N,N′-bis(2-hydroxyethyl)ethylenediamine (C₆H₁₆N₂O₂)] were reported herein. The IR spectra of these coordination compounds verified the formation of aforementioned complexes. The ground state of the paramagnetic electron in the Cu^II located in tetragonal distorted octahedral sites (D _4h ) was found to be d_x2−y2 for complex 2. As for complex 1, an EPR signal was not observed because of diamagnetic property of the Pt^II and momentary relaxation times of the Ni^II. All complexes followed identical decomposition mechanism in thermal analysis and thermal stabilities of complexes changed in the order of 1 > 4 > 3 > 2. Both 3 and 4 exhibit polymeric structure according to X-ray single structure analysis. While bishydeten coordinated with three donor atoms (N,N′, and O) in complex 3, it acts as a bidentate ligand (N, and N′) in complex 4. Magnetic properties of complexes 1–2 at 15–300 K temperature range were determined as antiferromagnetic with Weiss constants = −2.619 and −0.847 K respectively.