Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Tholen, Patrik; Peeples, Craig A.; Schaper, Raoul; Bayraktar, Ceyda; Erkal, Turan S.; Ayhan, Mehmet Menaf; Çoşut, Bünyemin; Beckmann, Jens; Yazaydın, A. Özgür; Wark, Michael; Hanna, Gabriel; Zorlu, Yunus; Yücesan, Gündoğ

doi:10.26434/chemrxiv.12003321.v1

Cited by 5 publications

(16 citation statements)

References 41 publications

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“…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.…”

Section: Resultssupporting

confidence: 81%

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

Keil¹,

Klein²,

Schmitt³

et al. 2020

Preprint

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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 via 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-H8TPPA and m-H8TPPA can monitor a wide range of metal ion concentrations via fluorescence titration and also via fluorescence decay curves. Cu and Zn-induced turn off fluorescence can be differentially reversed by the addition of common chelators. Both p-H8TPPA and m-H8TPPA readily pass the mammalian cellular membrane due to their amphipathic character as confirmed by confocal microscopic imaging of living enterocytes.

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Section: Resultssupporting

confidence: 81%

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

Keil¹,

Klein²,

Schmitt³

et al. 2020

Preprint

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“…[39][40][41] We also reported the first semiconductive permanently microporous hydrogen-bonded phosphonic acid framework (constructed using the p-H 8 TPPA linker) with a bandgap of 1.54 eV. [42] As summarized in a recent review article, [14] the number of threedimensional electrically conductive MOFs in the literature is limited. Thus, one of the important goals in MOF chemistry is to synthesize three-dimensional electrically conductive MOFs.…”

Section: Introductionmentioning

confidence: 99%

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

Zorlu

Wagner

Tholen

et al. 2022

Advanced Optical Materials

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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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“…[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.…”

Section: Semiconductive Phosphonate Mofsmentioning

confidence: 99%

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

Zorlu¹,

Tholen²,

Ayhan³

et al. 2021

Preprint

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Herein, we report the design and synthesis of a highly electrically conductive and microporous three-dimensional zinc-phosphonate metal-organic framework [Zn(Cu-p-H4TPPA)] ⋅2 (CH3)2NH2+ (designated as GTUB3), constructed using the 5,10,15,20‐tetrakis [p‐phenylphosphonic acid] porphyrin (p-H8TPPA) organic linker. GTUB3 has an indirect band gap of 1.64 eV and a high average electrical conductivity of 4 S/m, making it a rare example of an electrically conductive zinc metal-organic framework. The N2-accessible geometric surface area of GTUB3, as predicted by molecular simulations, is 671 m2/g. Owing to its simple, high-yield synthesis at low temperatures, porosity, and electrical conductivity, GTUB3 may be used as a low-cost electrode material in next generation phosphonate-supercapacitors.

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Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Cited by 5 publications

References 41 publications

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

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

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

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

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