Herein, we report a semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20-tetrakis[pphenylphosphonic acid] porphyrin (GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction. 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 DFT 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 humidity. The surface area was estimated to be 422 m 2 g −1 from grand canonical Monte Carlo simulations. XRD showed that GTUB5 is thermally stable under relative humidities of up to 90% at 90°C. These findings pave the way for a new family of organic, microporous, and semiconducting materials with high surface areas and high thermal stabilities.
Ao ne-dimensional nanotubularm etal-organic framework (MOF) [Ni(Cu-H 4 TPPA)]•2 (CH 3) 2 NH 2 + (H 8 TPPA = 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H 8 TPPAi s reported. The structure of this MOF,k nown as GTUB-4, was solved by using single-crystal X-ray diffractiona nd its geometrica ccessible surfacea rea was calculated to be 1102 m 2 g À1 ,m aking it the phosphonate MOF with the highest reporteds urface area. Due to the extended conjugation of its porphyrin core, GTUB-4 possesses narrow indirect and direct bandgaps (1.9 eV and 2.16 eV,r espectively) in the semiconductor regime. Thermogravimetric analysis suggests that GTUB-4 is thermally stable up to 400 8C. Owing to its high surface area, low bandgap, and high thermal stability, GTUB-4 could find applications as electrodes in supercapacitors. Metal-organic frameworks (MOFs) are microporous materials that contain well-defined micropores composed of organic and inorganic surfaces. [1-9] They have been used in applications ranging from gas adsorption, sequestration of greenhouse gases, [10, 11] catalysis, [12, 13] magnetism, [14-17] drug delivery, [18, 19] [c] K.
<p>We report the first semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20‐tetrakis[<i>p</i>‐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<sup>-6 </sup>S cm<sup>-1</sup> at 75 °C and 75 % relative humidity. The surface area of GTUB5’s hexagonal voids were estimated to be 422 m<sup>2</sup> g<sup>-1</sup> from grand canonical Monte Carlo simulations. XRD showed that GTUB5 is thermally stable under relative humidities of up to 90 % at 90 °C. These findings pave the way for a new family of microporous, organic, semiconducting materials with high surface areas and high thermal stabilities. Such materials could find applications in printed electronics, optoelectronics, and electrodes in supercapacitors.<br></p>
<p>We report the first one-dimensional tubular metal-organic framework (MOF) [Ni(Cu-H6TPPA)]∙2DMA (H8TPPA = 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) in the literature. The structure of this MOF, known as GTUB4, was solved using single crystal X-ray diffraction and its surface area was calculated to be 1102 m2/g, making it the phosphonate MOF with the highest reported surface area. GTUB4 also possesses a narrow indirect band gap of 1.9 eV and a direct band gap of 2.16 eV, making it a semiconducting MOF. Thermogravimetric analysis of GTUB4 suggests that it is thermally stable up to 400°C. Owing to its high surface area, low band gap, and thermal stability, GTUB4 could find applications as electrodes in supercapacitors.<br></p>
as paddle wheel patterns. [6,7] The ligandbinding modes around such molecular IBUs form large angles, ensuring separation between the organic struts and, in turn, resulting in large void spaces. [11] On the other hand, such separation limits the electrostatic interactions between the organic linkers. Therefore, traditional MOFs lack the required electron hopping and extended conjugation mechanisms between the bridging ligands to support electron mobility. [12][13][14] Although high surface area MOFs are ideal platforms to host electrons for supercapacitor applications, due to the lack of such mechanisms, conventional arylcarboxylate MOFs are generally known to be insulators. In addition to electrically conductive MOFs, photoluminescent MOFs have been the subject of active research due to their applications in sensing and light emitting diodes (LEDs). [15][16][17][18][19] In most cases, the photoluminescence is achieved either by the use of photoluminescent metal ions such as lanthanides, addition of fluorescent dyes to the MOF pores, or ligand exchange. [17,20] On the other hand, the photoluminescence in MOFs originating purely from the organic moieties is extremely rare and, to the best of our knowledge, there are no electrically conductive MOFs with high photoluminescence in the literature.Two-dimensional π-stacked MOFs based on ortho-diimine, ortho-dihydroxy, azolate, and thiolate metal-binding groups Herein, the design and synthesis of a highly photoluminescent and electrically conductive metal-organic framework [Zn{Cu-p-H 6 TPPA}]⋅2 [(CH 3 ) 2 NH](designated as GTUB3), which is constructed using the 5,10,15,20-tetrakis [p-phenylphosphonic acid] porphyrin (p-H 8 TPPA) organic linker, is reported. The bandgap of GTUB3 is measured to be 1.45 and 1.48 eV using diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy, respectively. The PL decay measurement yields a charge carrier lifetime of 40.6 ns. Impedance and DC measurements yield average electrical conductivities of 0.03 and 4 S m −1 , respectively, making GTUB3 a rare example of an electrically conductive 3D metal-organic framework. Thermogravimetric analysis reveals that the organic components of GTUB3 are stable up to 400 °C. Finally, its specific surface area and pore volume are calculated to be 622 m 2 g −1 and 0.43 cm 3 g −1 , respectively, using grand canonical Monte Carlo. Owing to its porosity and high electrical conductivity, GTUB3 may be used as a low-cost electrode material in next generation of supercapacitors, while its low bandgap and high photoluminescence make it a promising material for optoelectronic applications.
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