113919-79-2

Here we demonstrate that the utilization of 2,4,6-tris(4-pyridyl)pyridine (tpy) for metal-organic framework modification can greatly improve the photocatalytic performance for CO2 reduction. The electron-donating nature of tpy enables the charge transfer effect, which induces strong CO2 binding affinity, facilitates ?COOH formation and promotes CO2-to-CO conversion.

Metal-organic frameworks (MOFs) and MOF-based composites as luminescent sensors with excellent economic practicability and handy operability have attracted much attention. Herein, we designed and fabricated a porous Zn-based MOF, [Zn(OBA)2(L1)·2DMA]n [1; H2OBA = 4,4′-oxybis(benzoic acid), L1 = 2,4,6-tris(4-pyridyl)pyridine, and DMA = N,N-dimethylacetamide], with mixed nodes under solvothermal conditions, and the pore size of 5.9 ? was calculated from N2 adsorption isotherms by using a density functional theory model. The as-synthesized compound 1 is stable in different boiling organic solvents and water solutions with a wide pH range of 2-12 and exhibits intense luminescence emission at 360 nm under excitation of 290 nm. Significantly, compound 1 shows high selective detection of Fe3+, CrO42-, and Cr2O72- in aqueous solution even under the interference of other ions. Compound 1 can quickly sense these ions in a short time and has a striking sensitivity toward Fe3+ with an ultralow limit of detection (LOD) of 1.06 μM. The relatively low LODs for CrO42- and Cr2O72- are 3.87 and 2.37 μM, respectively, compared to the reported works. Meanwhile, compound 1 can be reused to detect Fe3+, CrO42-, and Cr2O72- six times by simple regeneration. Considering the practicability, a mixed-matrix membrane (MMM) incorporated compound 1 and poly(methyl methacrylate) has been constructed. This MMM displays quick detection of Fe3+, CrO42-, and Cr2O72- and prompt regeneration by lifting from the analyte. This useful MMM shows a comparable LOD below 4.35 μM for these ions. This work presents a cost-effective Zn-based MOF as a functional platform for simple but useful sensing of Fe3+, CrO42-, and Cr2O72- in aqueous solution.

Using a strategy of layering solvents and solutions of ligands and metal salts under ambient conditions, we observe the assembly of a discrete molecular metallohexacycle from ZnCl2 and 4′-(4-ethynylphenyl)-4, 2′:6′,4′′-terpyridine, polycatenated, triply interlocked metallocapsules from ZnI2 and 4′-(4-pyridyl)-4,2′: 6′,4′′-terpyridine, and 1-dimensional coordination polymers from either ZnCl2 or ZnI2 with 4′-{4-(3- chloropyridyl)}-4,2′:6′,4′′-terpyridine. On the basis of these studies and a comparison with related structures in the literature, we urge crystal engineers to be wary of drawing conclusions about self-assembly algorithms in solution using data from single crystal determinations. The Royal Society of Chemistry 2011.

The novel compounds 1,1''-dimethylterpyridiniumdiperchlorate (6), 1,1',1''-trimethylterpyridiniumtriperchlorate (7) and 1,1'',1'''-trimethylquaterpyridiniumtriperchlorate (8) were synthesized. (6) and (8) give, upon reduction with Zn, stable radical cations which were investigated by NMR-, vis- and ESR-spectroscopy and cyclovoltammogrammes.

Micro-/nanocapsules have received substantial attention due to various potential applications for storage, catalysis, and drug delivery. However, their conventional enclosed non-/polycrystalline walls pose huge obstacles for rapid loading and mass diffusion. Here, we present a new single-crystal capsular-MOF with openings on the wall, which is carefully designed at the molecular level and constructed from a crystal-structure transformation. This rare open-capsule MOF can easily load the largest amounts of sulfur and iodine among known MOFs. In addition, derived from capsular-MOF and melamine through pyrolysis-phosphidation, we fabricated a nitrogen-doped capsular carbon-based framework with iron-nickel phosphide nanoparticles immobilized on capsular carbons interconnected by plentiful carbon nanotubes. Benefiting from synergistic effects between the carbon framework and highly surface-exposed phosphide sites, the material exhibits efficient multifunctional electrocatalysis for oxygen evolution, hydrogen evolution, and oxygen reduction, achieving well-qualified assemblies of an overall water splitting (low potential of 1.59 V at 10 mA·cm-2) and a rechargeable Zn-air battery (high peak power density of 250 mW·cm-2 and excellent stability for 500 h), which afford remarkably practical prospects over previously known electrocatalysts.

The presented study is the first report of the synthesis of terpyridines in the presence of a nanomagnetic catalyst instead of harmful reagents. Herein, Fe3O4&at;O2PO2(CH2)2NH3+CF3CO2- as a retrievable nanocatalyst with magnetic properties was applied for the multi-component reaction between acetylpyridine derivatives (2 or 3 or 4-isomer), aryl aldehydes and ammonium acetate under conventional heating conditions in the absence of any solvent. The derived terpyridines were obtained with acceptable yields and brief reaction times via a cooperative vinylogous anomeric based oxidation route. Fe3O4&at;O2PO2(CH2)2NH3+CF3CO2- showed a high capability for recovery and reuse in the mentioned reaction.

Micro-/nanocapsules have received substantial attention due to various potential applications for storage, catalysis, and drug delivery. However, their conventional enclosed non-/polycrystalline walls pose huge obstacles for rapid loading and mass diffusion. Here, we present a new single-crystal capsular-MOF with openings on the wall, which is carefully designed at the molecular level and constructed from a crystal-structure transformation. This rare open-capsule MOF can easily load the largest amounts of sulfur and iodine among known MOFs. In addition, derived from capsular-MOF and melamine through pyrolysis-phosphidation, we fabricated a nitrogen-doped capsular carbon-based framework with iron-nickel phosphide nanoparticles immobilized on capsular carbons interconnected by plentiful carbon nanotubes. Benefiting from synergistic effects between the carbon framework and highly surface-exposed phosphide sites, the material exhibits efficient multifunctional electrocatalysis for oxygen evolution, hydrogen evolution, and oxygen reduction, achieving well-qualified assemblies of an overall water splitting (low potential of 1.59 V at 10 mA·cm-2) and a rechargeable Zn-air battery (high peak power density of 250 mW·cm-2 and excellent stability for 500 h), which afford remarkably practical prospects over previously known electrocatalysts.

A series of 2,4,6-tripyridyl pyridines were synthesized, and evaluated for their antitumor cytotoxicity, topoisomerase I and II inhibitory activity. From the eighteen prepared compounds, compounds 10-12 have shown better or similar cytotoxicity against several human cancer cell lines as compared to 2,2':6',2''- terpyridine and doxorubicin. Especially, compound 10 exhibited the most potent cytotoxicity better than positive controls. Structure-activity relationship study indicated that 2,2':6',2''-terpyridine skeleton has an important role in displaying significant cytotoxicity against several human cancer cell lines.

Two novel Zn(II) coordination polymers, [Zn(2-pytpy)(fum)] n·nH2O (1) and [Zn6(4-pytpy) 3(mal)4]n·5n(H2O) (2), (2-pytpy = 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine, 4-pytpy = 4′-(4-pyridyl)-4,2′:6′,4″-terpyridine, H 2fum = fumaric acid and H2mal = malic acid) have been hydrothermally synthesized and structurally characterized. Notably, in situ ligand reactions occur in the formation of complexes 1 and 2, in which maleic acid is converted into fumaric acid and malic acid, respectively. Complex 1 is a 1D infinite chain structure, which is extended into a supramolecular layer by intermolecular π...π stacking interactions. Complex 2 is a 3D network structure, in which the bidentate-bridging 4-pytpy ligands link the layers based on the tetranuclear Zn(II) subunits to form the (4,10)-connected network. The luminescent properties of 1 and 2 have been investigated with emission spectra and UV-Vis diffuse reflectance spectra in the solid state. Additionally, these two complexes possess great thermal stabilities.