Polyphosphonate covalent organic frameworks.

Herein, we report polyphosphonate covalent organic frameworks (COFs) constructed via P-O-P linkages. The materials are synthesized via a single-step condensation reaction of the charge-assisted hydrogen-bonded organic framework, which is constructed from phenylphosphonic acid and 5,10,15,20-tetrakis[p-phenylphosphonic acid]porphyrin and is formed by simply heating its hydrogen-bonded precursor without using chemical reagents. Above 210 °C, it becomes an amorphous microporous polymeric structure due to the oligomerization of P-O-P bonds, which could be shown by constant-time solid-state double-quantum P nuclear magnetic resonance experiments.

A 2,7-dichlorofluorescein derivative to monitor microcalcifications.

Herein, we report the crystal structure of 2,7-dichlorofluorescein methyl ester (DCF-ME) and its fluorescence response to hydroxyapatite binding. The reported fluorophore is very selective for staining the bone matrix and provides turn-on fluorescence upon hydroxyapatite binding. The reported fluorophore can readily pass the cell membrane of the C2C12 cell line, and it is non-toxic for the cell line.

Exceptionally Stable And Super-Efficient Electrocatalysts Derived From Semiconducting Metal Phosphonate Frameworks.

Two new isostructural semiconducting metal-phosphonate frameworks are reported. Co [1,4-NDPA] and Zn [1,4-NDPA] (1,4-NDPA is 1,4-naphthalenediphosphonate) have optical bandgaps of 1.7 eV and 2.

A New Family of Layered Metal-Organic Semiconductors: Cu/V-Organophosphonates.

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H O) V(µ-O)(PPA) ] (where PPA is phenylphosphonate). The crystal structure of [Cu(H O) V(µ-O)(PPA) ] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H O) V(µ-O)(PPA) ] has an indirect band gap of 2.

Coordination-Induced Band Gap Reduction in a Metal-Organic Framework.

Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal-organic framework (MOF) with the composition Cu (H -MTPPA)  ⋅ 2 NMP (H -MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.

Arylphosphonate-Tethered Porphyrins: Fluorescence Silencing Speaks a Metal Language in Living Enterocytes*.

We report the application of a highly versatile and engineerable novel sensor platform to monitor biologically significant and toxic metal ions in live human Caco-2 enterocytes. The extended conjugation between the fluorescent porphyrin core and metal ions through aromatic phenylphosphonic acid tethers generates a unique turn off and turn on fluorescence and, in addition, shifts in absorption and emission spectra for zinc, cobalt, cadmium and mercury. The reported fluorescent probes p-H TPPA and m-H TPPA can monitor a wide range of metal ion concentrations via fluorescence titration and also via fluorescence decay curves.

Semiconductive microporous hydrogen-bonded organophosphonic acid frameworks.

Herein, we report a semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction. A narrow band gap of 1.

A Nanotubular Metal-Organic Framework with a Narrow Bandgap from Extended Conjugation*.

A one-dimensional nanotubular metal-organic framework (MOF) [Ni(Cu-H TPPA)]⋅2 (CH ) NH (H TPPA=5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H TPPA is reported. The structure of this MOF, known as GTUB-4, was solved by using single-crystal X-ray diffraction and its geometric accessible surface area was calculated to be 1102 m  g , making it the phosphonate MOF with the highest reported surface area. Due to the extended conjugation of its porphyrin core, GTUB-4 possesses narrow indirect and direct bandgaps (1.

Phosphonate Metal-Organic Frameworks: A Novel Family of Semiconductors.

Herein, the first semiconducting and magnetic phosphonate metal-organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner-sharing copper dimers. The solid-state UV-vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)-calculated bandgap of 1.

Fluorescent Arylphosphonic Acids: Synergic Interactions between Bone and the Fluorescent Core.

Herein, we report the third generation of fluorescent probes (arylphosphonic acids) to target calcifications, particularly hydroxyapatite (HAP). In this study, we use highly conjugated porphyrin-based arylphosphonic acids and their diesters, namely 5,10,15,20-tetrakis[m-(diethoxyphosphoryl)phenyl]porphyrin (m-H TPPA-OEt ) and 5,10,15,20-tetrakis [m-phenylphosphonic acid]porphyrin (m-H TPPA), in comparison with their positional isomers 5,10,15,20-tetrakis[p-(diisopropoxyphosphoryl)phenyl]porphyrin (p-H TPPA-iPr ) and 5,10,15,20-tetrakis [p-phenylphosphonic acid]porphyrin (p-H TPPA), which have phosphonic acid units bonded to sp carbon atoms of the fluorescent core. The conjugation of the fluorescent core is thus extended to the (HAP) through sp -bonded -PO H units, which generates increased fluorescence upon HAP binding.

Alkali Phosphonate Metal-Organic Frameworks.

A new family of porous metal-organic frameworks (MOFs), namely alkali phosphonate MOFs, is reported. [Na Cu(H TPPA)]⋅(NH (CH ) ) (GTUB-1) was synthesized using the tetratopic 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H -TPPA) linker with planar X-shaped geometrical core. GTUB-1 is composed of rectangular void channels with BET surface area of 697 m  g .

Correction: A cobalt arylphosphonate MOF - superior stability, sorption and magnetism.

Correction for 'A cobalt arylphosphonate MOF - superior stability, sorption and magnetism' by Yunus Zorlu et al., Chem. Commun.

A cobalt arylphosphonate MOF - superior stability, sorption and magnetism.

We report a novel metal-organic framework (MOF) based on a cobalt arylphosphonate, namely, [Co2(H4-MTPPA)]·3NMP·H2O (1·3NMP·H2O), which was prepared solvothermically from the tetrahedral linker tetraphenylmethane tetrakis-4-phosphonic acid (H8-MTPPA) and CoSO4·7H2O in N-methyl-2-pyrrolidone (NMP). Compound 1 has the highest porosity (BET surface area of 1034 m2 g-1) ever reported for a MOF based on an aryl phosphonic acid linker. The indigo blue crystals of 1·3NMP·H2O are composed of edge-shared eight-membered Co2P2O4 rings, and are thermally very stable up to 500 °C.

A potential Cu/V-organophosphonate platform for tailored void spaces via terpyridine mold casting.

The reaction of appropriate copper and vanadium salts with tetratopic methane tetra-p-phenylphosphonic acid (MTPPA) in the presence of 2,2':6':2''-terpyridine (terpy) yielded the three-dimensional bimetallic copper vanadium phosphonate framework [{Cu(terpy)}Cu(VO)(MTPPA-H)]·4HO (1). Terpy has no net contribution to the three-dimensional structure providing a potential platform for void space formation via mold-casting. The structure was characterized by single-crystal X-ray diffraction and thermogravimetric analysis (TGA).

Influence of alkyl chain length on the surface activity of antibacterial polymers derived from ROMP.

The purpose of this study is to understand the antibacterial properties of cationic polymers on solid surfaces by investigating the structure-activity relationships. The polymer synthesis was carried via ring opening metathesis polymerization (ROMP) of oxanorbornene derivatives. Modulation of molecular weights and alkyl chain lengths of the polymers were studied to investigate the antibacterial properties on the glass surface.

Solid state coordination chemistry of the copper(ii)-terpyridine/oxovanadium organophosphonate system: hydrothermal syntheses, structural characterization and magnetic properties.

The hydrothermal reactions of CuSO4.5H2O, Na3VO4, 2,2':6':2''-terpyridine (terpy), and the appropriate organophosphonate ligand yield a series of materials of the Cu(ii)-terpy/oxovanadium organophosphonate family. The complexes exhibit distinct structures spanning one-, two- and three-dimensions and exhibiting diverse oxovanadium building blocks.