Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Abstract

We report the first semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20-tetrakis[p-15 phenylphosphonic acid] porphyrin (known as GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction (XRD). A narrow band gap of 1.56 eV was extracted from a UV-Vis spectrum of pure GTUB5 crystals, in excellent agreement with the 1.65 eV band gap obtained from density functional theory calculations. The same band gap was also measured for GTUB5 in DMSO.The proton conductivity of GTUB5 was measured to be 3.00 ´ 10 -6 S cm -1 at 75 °C and 75 % relative 20 humidity. The surface area of GTUB5's hexagonal voids were estimated to be 422 m 2 g -1 from grand

Arylphosphonate-Tethered Porphyrins: Fluorescence Silencing Speaks a Metal Language in Living Enterocyte

“…1), were pretreated with various bivalent metal ions at a pH close to the cellular milieu (pH 7.4) before recording absorption and fluorescence spectra. The visible absorption of both sensors in the buffer-control treatment showed maxima in the range of 380-430 nm, with a typical Soret peak at around 416 nm, already observed in our recent studies [36,44] and also by others [45] . Ca 2+ or Mg 2+ treatment did not shift the position of the Soret maximum, but slightly raised the intensity of the absorption spectrum causing a higher fluorescence, characteristic for non-ratiometric metal-ON fluorescence sensors.…”

A proton conductive hydrogen-bonded framework incorporating 18-crown-6-ether and dicarboxy-o-terphenyl moieties

“…To date, some HOFs are reported to show proton conductivity. [26][27][28][29][30][31][32] However, proton conductive HOFs based on crown ethers are hitherto unknown.…”

High Electrical Conductivity in Three-Dimensional Porphyrin-Phosphonate Metal Organic-Frameworks

“…[33][34][35] In a related study, we reported the first semiconductive permanently microporous hydrogen-bonded phosphonic acid framework (constructed using the p-H 8 TPPA linker) with a band gap of 1.54 eV. 36 To the best of our knowledge, no semiconductive zincphosphonate MOFs have been reported in the literature. Thus, in this work, we used the polyaromatic porphyrin core with zinc IBUs to synthesize a semiconductive zinc-phosphonate MOF known as GTUB3.…”