Five Mesoporous Lanthanide Metal-Organic Frameworks: Syntheses, Structures, and Fluorescence Sensing of Fe3+, Cr2O72-, and H2O2 and Electrochemical Sensing of Trinitrophenol.

When a multicarboxylate aromatic ligand, 3,5-di(2',4'-dicarboxylphenyl)benzoic acid (H5L), was employed, five structurally similar lanthanide metal-organic frameworks (Ln-MOFs), {[Pr10L6(OH)3Cl(H2O)6]·4C2H8N}n (1), {[Nd10L6(OH)4 (H2O)9]·4C2H8N}n (2), {[Gd10L6(OH)4(H2O)3]·4C2H8N}n (3), {[Ho10L6(OH)4 (H2O)3]·4C2H8N}n (4) and {[Er10L6(OH)4(H2O)6]·4C2H8N}n (5), were synthesized and characterized. Single-crystal X-ray structural analyses disclosed that all five Ln-MOFs crystallize in the trigonal R3 space group. They have three-dimensional mesoporous structure featuring the coexistence of binuclear and tetranuclear species as inorganic building units. The mesoporous structure of 3 was verified by the gas adsorption experiment of N2. Fluorescence analysis showed that 3 can selectively detect Fe3+, Cr2O72-, and H2O2; furthermore, it can be used for the electrochemical detection of trinitrophenol. With the merit of an excellent highly sensitive detection performance, 3 has unpredictable application prospects in future research fields.

Three-dimensional frameworks based on dodecanuclear Dy-hydroxo wheel cluster with slow relaxation of magnetization.

Two new heterometallic coordination polymers, [Na4Ln12(stp)8(OH)16(H2O)12]·10H2O [Ln = Dy (1) and Ho (2)], have been prepared from monosodium 2-sulfoterephthalate (NaH2stp), dysprosium acetate, or holmium acetate. They are isostructural, possessing a [Ln12(µ3-OH)16](20+) wheel-cluster core based on four vertex-sharing cubane-like [Ln4(µ3-OH)4](8+) units. The Ln12 cores are linked by stp ligands into a three-dimensional (3D) architecture. Magnetic studies indicate that complex 1 exhibits slow relaxation of magnetization, and it can be regarded as the first 3D coordination assembly of a Dy12 cluster single-molecule magnet.

Zn-coordination polymers for fluorescence sensing various contaminants in water.

Luminescent coordination polymers (LCPs) have garnered significant attention from researchers as promising materials for detecting contaminants. In this paper, three new LCPs ([Zn(tib)(opda)]n⋅H2O (1), [Zn3(tib)2(mpda)3]n⋅5H2O (2), [Zn (tib)(ppda)]n⋅H2O (3)) with different structures (LCP 1-3: 1D, 2D, 1D) using phenylenediacetic acid isomers and 1,3,5-tris (1-imidazolyl) benzene (tib) are synthesized. The specific surface areas (BET) of LCP 1-3 are 4 m2/g, 19 m2/g, and 13 m2/g respectively. LCP 1-3 exhibit excellent fluorescence properties and can serve as fluorescent probe for the detection of inorganic contaminants and organic contaminants. Due to the large BET of LCP 2, the detection limits for trace analytes surpass those of LCP 1 and 3. The detection limits of LCP 2 for Fe3+, nitrobenzene (NB), chloramphenicol (CAP), and pyrimethanil (PTH) are 8.3 nM, 0.016 µM, 0.19 µM, and 0.032 µM, respectively, and the fluorescence quenching rates are 98.6 %, 98.8 %, 92.3 %, and 98.8 %, respectively. These values outperform most reported in the literature. The quantum yields of LCP 1-3 are 11.84 %, 25.22 %, 22.00 % respectively. Real sample testing of LCP 1-3 reveals favorable performance, where spiked recoveries of LCP 2 for the detection of pyrimethanil in grape skins ranged from 99.62 % to 119.3 % with a relative standard deviation (RSD) of 0.627 % to 4.56 % (n = 3). The fluorescence quenching mechanism was attributed to a combination of photoelectron transfer (PET), resonance energy transfer (RET), and competitive absorption (CA). This study advances the application of LCPs in luminescence sensing and contributes to the expansion of novel materials for detecting environmental pollutants.

Water-Stable Cd-MOF with fluorescent sensing of Tetracycline, Pyrimethanil, abamectin benzoate and construction of logic gate.

Due to the indiscriminate abuse of pesticides and antibiotics has caused serious threats to the environment and human and animal bodies, the detection of antibiotics and pesticides has attracted widespread attention in recent years. Herein, a novel 2D Cd (II)-MOF, [Cd(L)0.5(1,2-bimb)] (Cd-L-1,2-bimb), [H4L = 1, 1'-ethylbiphenyl -3, 3', 5, 5'- tetracarboxylic acid, 1, 2-bimb = 1, 2-bis[(1H-imidazol-1-yl) methyl] benzene] is synthesized. Cd-L-1,2-bimb has excellent stability in different organic solvents and in the range of pH 1.1-12.5. Cd-L-1,2-bimb exhibits high selectivity, high sensitivity, and fast luminescent response to pesticides [pyrimethanil (PTH, LOD = 2.2 µM) and abamectin benzoate (AMB, LOD = 2.39 µM)] and antibiotic contaminants tetracycline (TET, LOD = 0.13 µM). Cd-L-1,2-bimb displays discriminative fluorescence when detecting AMB and PTH, and is an implication logic gate. Finally, the possible detection mechanism of Cd-L-1,2-bimb toward different pollutants is also further investigated. This MOF-based multifunctional sensor opens up new prospects for environmental monitors.

Highly selective detecting Aspartic acid, detecting Ornidazole and information encryption and decryption supported by a heterometallic anionic Cd (II)-K (I)-MOF.

A highly stable heterometallic MOF, {[(Me2NH2)2]·[Cd2K2(L)2(H2O)]}n (H4L = terphenyl-2, 2', 4, 4'-tetracarboxylic acid) (1), was synthesized. 1 featuring one-dimensional channels can efficiently detect Aspartic acid with a low limit of detection (LOD) value (2.5 µM). More interestingly, 1 can encapsulate Eu3+ and sensitize the visible-emitting characteristic fluorescence of Eu3+ in aqueous solution. Then, Eu3+@CdK-MOF is found to be an excellent fluorescence sensor for the detection of Ornidazole (ODZ) and the portable ODZ test paper is also successfully designed. Eu3+@CdK-MOF can also be used as fluorescent ink to write some words. The words can be hidden when treated with acid vapor and then the words can be restored when treated with alkaline vapor. More importantly, the hidden information can be read repeatedly. Therefore, this reversible light-emitting and reusable property have great potential for development in information encryption and decryption and information storage.

Novel Multifunctional Samarium-Organic Framework for Fluorescence Sensing of Ag+, MnO4 -, and Cimetidine and Electrochemical Sensing of o-Nitrophenol in Aqueous Solutions.

A novel Sm-metal-organic framework (MOF) sensor with the molecular formula Sm8(HDBA)6·H2O has been prepared based on a penta-carboxyl organic ligand (H5DBA = 3,5-di(2',4'-dicarboxylphenyl)benzoic acid) and samarium nitrate under solvothermal conditions. Sm-MOF is characterized by single-crystal X-ray diffraction analysis, elemental analysis, thermogravimetric analysis, and powder X-ray diffraction analysis. Structural analysis shows that the dimer metal units are alternately connected to form a one-dimensional chain, and this chain is connected by the bridging carboxyl oxygen of the ligand H5DBA to form a two-dimensional double-layer plane, which then expands into a three-dimensional microporous framework. Fluorescence detection studies show that Sm-MOF can detect Ag+ ions, MnO4 - anions, and cimetidine tablets with high sensitivity and selectivity and can also be used to electrochemically detect o-nitrophenol in water. High-sensitivity detection capability of the Sm-MOF can enrich the application of samarium complexes in multifunctional sensors.

Tetra-aqua-bis-(1,10-phenanthroline-κN,N')strontium 5,5'-diazene-diyl-ditetra-zolide.

The title complex, [Sr(C(12)H(8)N(2))(2)(H(2)O)(4)](C(2)N(10)), contains an [Sr(phen)(2)(H(2)O)(4)](2+) cation (phen is 1,10-phenanthroline) and a 5,5'-diazenediylditetra-zolide anion (site symmetry 2). The Sr(2+) cation (site symmetry 2) is coordinated by four N atoms from two chelating phen and four water mol-ecules. In the crystal structure, the water mol-ecules and the N atoms in the tetra-zolide rings form an extensive range of O-H⋯N hydrogen bonds which link the complex into a two-dimensional structure. An adjacent layer further yields a three-dimensional supramolecular network by offset face-to-face π-π stacking inter-actions of the phen ligands [with centroid-centroid distances of 3.915 (2) and 4.012 (2) Å]. The two bridging N atoms of the anion are equally disordered about the twofold rotation axis.

A Multifunctional Tb-MOF Detector for H2O2, Fe3+, Cr2O7 2-, and TPA Explosive Featuring Coexistence of Binuclear and Tetranuclear Clusters.

A novel three-dimensional microporous terbium(III) metal-organic framework (Tb-MOF) named as [Tb10 (DBA)6(OH)4(H2O)5]·(H3O)4 (1), was successfully obtained by a solvothermal method based on terbium nitrate and 5-di(2',4'-dicarboxylphenyl) benzoic acid (H5DBA). The Tb-MOF has been characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetry, and fluorescence properties, and the purity was further confirmed by powder X-ray diffraction (PXRD) analysis. Structural analysis shows that there are two kinds of metal cluster species: binuclear and tetranuclear, which are linked by H5DBA ligands in two µ7 high coordination fashions into a three-dimensional microporous framework. Fluorescence studies show that the Tb-MOF can detect H2O2, Fe3+, and Cr2O7 2- with high sensitivity and selectivity and can also be used for electrochemical detection of exposed 2,4,6-trinitrophenylamine (TPA) in water. The highly selective and sensitive detection ability of the Tb-MOF might make it a potential multifunctional sensor in the future.

Dense π-stacking of flexible ligands fixed in interpenetrating Zn(ii) MOF exhibiting long-lasting phosphorescence and efficient carrier transport.

Three-fold interpenetrating Zn(ii) MOF with the dense π-stacking of flexible ligands exhibit long-lived phosphorescence emission up to 91 ms at room temperature. Photoelectric measurements show efficient electro-hole separation based on the long lifetime of triplet state exciton.

A novel 3D Cd(ii) coordination polymer generated via in situ ligand synthesis involving C-O ester bond formation.

A novel 3D Cd(ii) coordination polymer {[Cd(ddpa)(2,2'-bpy)]·H2O} n (1) (H2ddpa = 5,10-dioxo-5,10-dihydro-4,9-dioxapyrene-2,7-dicarboxylic acid, 2,2'-bpy = 2,2'-bipyridine) is hydrothermally synthesized in situ, and the influencing factors and mechanism for the in situ reaction are briefly discussed. The synthesis of 1 requires the formation of a new C-O ester bond. This current study confirms that metal ions and N-donor ligands play important roles in the domination of the in situ ligand from 6,6'-dinitro-2,2',4,4'-biphenyltetracarboxylic acid (H4dbta). Furthermore, the structure, thermal stability and photoluminescent property of 1 are also investigated.

Effects of template molecules on the structures and luminescence intensities of a series of porous Tb-MOFs based on the 2-nitroterephthalate ligand.

Four novel porous Tb(iii) metal-organic frameworks (Tb-MOFs) have been designed and prepared hydrothermally from 2-nitroterephthalate (2-H2ntp), namely {[Tb(2-ntp)1.5(H2O)]·H2O} n (1), {[Tb(2-ntp)2(H2O)]·4,4'-Hbipy} n (2), {[Tb(2-ntp)2(H2O)]·2,4-Hbipy} n (3), and {[Tb(2-ntp)2(H2O)]·(1,4-H2bbi)0.5} n (4) (4,4'-bipy = 4,4'-bipyridine; 2,4-bipy = 2,4-bipyridine; 1,4-bbi = 1,4-bisbenzimidazole). X-ray diffraction structural analyses show these Tb-MOFs are porous and are based on Tb3+ ions and 2-nitroterephthalate, in which water molecules (1) or protonated N-donor ligands (2-4) exist as templates. The fluorescence properties of complexes 1-4 could be associated with the characteristic peaks of Tb(iii) ions, and the existence of different guest molecules affects the intensities of peaks, which means that these could be potential fluorescence materials, with intensities adjusted using guests.

Self-assembly, crystal structures, and properties of metal-2-sulfoterephthalate frameworks based on [M4(µ3-OH)2]6+ clusters (M = Co, Mn, Zn and Cd).

Hydro- and solvo-thermal reactions of d-block metal ions (Mn(2+), Co(2+), Zn(2+) and Cd(2+)) with monosodium 2-sulfoterephthalate (NaH(2)stp) form six 3D coordination polymers featuring cluster core [M(4)(µ(3)-OH)(2)](6+) in common: [M(2)(µ(3)-OH)(stp)(H(2)O)] (M = Co (1), Mn (2) and Zn (3)), [Zn(2)(µ(3)-OH)(stp)(H(2)O)(2)] (4), [Zn(4)(µ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O (5) and [Cd(2)(µ(3)-OH)(stp) (bpp)(2)]·H(2)O (6) (stp = 2-sulfoterephthalate, bpy = 4,4'-bipyridine and bpp = 1,3-di(4-pyridyl)propane). All these coordination polymers were characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric and elemental analysis. Complexes 1-3 are isostructural coordination polymers with 3D frameworks based on the chair-like [Zn(4)(µ(3)-OH)(2)](6+) core and the quintuple helixes. In complex 4, there exist double helixes in the 3D framework based on the chair-like cluster cores. Complex 5 possesses a 2-fold interpenetration structure constructed from boat-like cluster core and the bridging ligands stp and bpy. For complex 6, the chair-like cluster cores and stp ligands form a 2D (4,4) network which is further pillared by bpp linkers to a 3D architecture. Magnetic studies indicate that complex 1 exhibits magnetic ordering below 4.9 K with spin canting, and complex 2 shows weak antiferromagnetic coupling between the Mn(II) ions with g = 2.02, J(wb) = -2.88 cm(-1), J(bb) = -0.37 cm(-1). The fluorescence studies show that the emissions of complexes 3-6 are attributed to the ligand π-π* transition.

Nanoporous lanthanide-carboxylate frameworks based on 5-nitroisophthalic acid.

The reactions of lanthanide nitrates with 5-nitroisophthalic acid (ab. 5-H(2)nip) in DMF and ethanol (1 : 1) mixed solution gave rise to three nanoporous lanthanide polymers, {[Ln(2)(5-nip)(3)(DMF)(4)](DMF)(2)}(n) (Ln = Nd (), Dy (), Ho (), 5-nip = 5-nitroisophthalate). Single-crystal X-ray diffraction analyses reveal that they are isomorphous and feature three-dimensional metal-organic frameworks with two-dimensional intersecting channels occupied by guest DMF molecules constructed from the linkage of dimer Ln(2)C(6)O(12) SBUs and 5-nip ligands. The guest DMF molecules can be reversibly removed from as identified using TGA-DSC and PXRD. The heat of adsorption of the guest-free sample of with DMF was measured with a value of 10.3 kJ mol(-1) by an RD496-III type microcalorimeter. In addition, the photoluminescent property of was investigated.