From Tetrahedral Tetraphosphonic Acids E[p
-C6
H4
P(O)(OH)2
]4
 (E=C, Si) to Porous Cu- and Zn-MOFs with Large Surface Areas

Schütrumpf, Alexandra; Bulut, Aysun; Hermer, Nele; Zorlu, Yunus; Kirpi, Erdoğan; Stock, Norbert; Yazaydın, A. Özgür; Yücesan, Gündoğ; Beckmann, Jens

doi:10.1002/slct.201700573

Cited by 25 publications

(29 citation statements)

References 36 publications

(6 reference statements)

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“…The phosphonic acid functional group has two protons and one oxygen from the P=O bond, which allow it to form multiple hydrogen bonds with other phosphonic acid groups and thereby stabilize the resulting HOF. Interestingly, the unique structure and multiple metal binding modes of the phosphonic acid functional group have led to some of the most thermally [34,[43][44][45][46] and chemically stable [34,[47][48][49] MOFs in 5 the literature. The phosphonic acid functional group R-PO3H2 involves two deprotonation modes with pKa values of 1.7 and 7.4, respectively.…”

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confidence: 99%

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Tholen¹,

Peeples²,

Schaper³

et al. 2020

Preprint

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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

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confidence: 99%

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Tholen¹,

Peeples²,

Schaper³

et al. 2020

Preprint

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“…From the tetraphosphonic acids, 6 was described previously, whereas 7 and 8 are new compounds. The tetrabiphenylsilane tetrakis‐4‐phosphonic acid ( 7 ) is a topological analog of tetraphenylmethane tetrakis‐4‐phosphonic acid and tetraphenylsilane tetrakis‐4‐phosphonic acid, which was recently used for the preparation of Cu and Zn‐based MOFs showing very high surface areas , . Notably, both tetraphosphonic acids were prepared from the same starting material, namely tetrakis(4‐bromophenyl)silane.…”

Section: Resultsmentioning

confidence: 99%

“…Up to the early 2000s, most metal‐organophosphonates possessed highly dense pillared‐layered and lamellar structures because their syntheses relied on structurally flexible alkylphosphonate linkers . More recently, with the introduction of the rigid tetratopic arylphosphonate linkers, such as the square planar tetra(4‐phosphonophenyl)porphyrin and the tetrahedral tetraphenylmethane tetrakis‐4‐phosphonic acid precluded the formation of dense 2D metal oxide layers. Their introduction has increased the distances between the organophosphonate adhesive units and favored the formation of metal oxide clusters and stable one‐dimensional inorganic building units to form one‐dimensional hexagonal void channels or porous diamandoid networks.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Some Di‐ and Tetraphosphonic Acids by Suzuki Cross‐Coupling

Schütrumpf

Duthie

Lork

et al. 2018

Zeitschrift anorg allge chemie

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Five diphosphonic acids, namely, benzene-1,4-bis-p-phenylphosphonic acid (1), anthracene-9,10-bis-p-phenylphosphonic acid (2), benzene-1,2-bis-p-phenylphosphonic acid (3), benzene-1,3-bis-p-phenylphosphonic acid (4), and biphenyl-4,4Ј-bis-p-phenylphosphonic acid (5) as well as three tetraphosphonic acids, namely, benzene-1,2,4,5tetrakis-p-phenylphosphonic acid (6), tetrabiphenylsilane tetrakis-4phosphonic acid (7), and pyrene-1,3,6,8-tetrakis-p-phenylphosphonic acid (8) and their dimethyl esters 1a-8a were prepared via Suzuki cross-coupling reactions involving p-dimethylphosphonatophenyl-1136 were recorded, which showed single resonances for 2, 4, and 7 at δ = 18.6, 16.2, and 18.7 ppm, respectively.

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“…With this type of rigid ligand, high catalytic and proton conductivities, up to 2.58 × 10 −2 S·cm −1 , were found [16]. Tetraphosphonates with a tetrahedral structure have been also published [17,18]. Recently, a review on tetraphenylmethane (TPPM) and tetraphenylsilane (TPPSi) as building units of coordination polymers has been reported [19].…”

Section: Introductionmentioning

confidence: 92%

High-Throughput Synthesis of Pillared-Layered Magnesium Tetraphosphonate Coordination Polymers: Framework Interconversions and Proton Conductivity Studies

et al. 2018

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Novel pillared-layered framework materials were synthesized by high-throughput or microwave-assisted methodology that contain Mg2+ and the zwitterionic linker HDTMP (hexamethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic acid)). Three compounds were structurally characterized by X-ray powder diffraction. In the compound {Mg[(HO3PCH2)2N(CH2)6N(CH2PO3H2)2]·(H2O)}n(1), obtained at 140 °C by hydrothermal or microwave-assisted reaction, the layers are built by isolated Mg2+ octahedra coordinated by oxygen atoms from six different zwitterionic HDTMP ligands. Each amino-bis(methylenephosphonate) moiety links three Mg2+ ions, bridging two of them through one phosphonate group and connecting the third polyhedron in a monodentate fashion. In Compound 2, {Mg[(HO3PCH2)2N(CH2)6N(CH2PO3H2)2]}n, hydrothermally synthesized at 180 °C, the layers are composed of bidentate amino-bis(methylenephosphonate) moieties connected to three Mg2+ ions, with one of the phosphonate groups acting as a bridging ligand. Various subtle structural changes are noted for the other two compounds. Thermodiffraction of 1 reveals that a crystalline-to-crystalline phase transformation occurs concomitantly with its dehydration, leading to a new anhydrous phase, namely, {Mg[(HO3PCH2)2N(CH2)6N(CH2PO3H2)2]}n(1deh). This process is fully reversible upon equilibrating the solid at room temperature. The reported compounds can adsorb ammonia and CO2. Compound 1 exhibits a moderate proton conductivity, ~1.5 × 10−5 S·cm−1 at 80 °C and 95% RH, that increases a half order of magnitude after experiencing a complete dehydration/rehydration process, 1→1deh→1.

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From Tetrahedral Tetraphosphonic Acids E[p -C₆ H₄ P(O)(OH)₂ ]₄ (E=C, Si) to Porous Cu- and Zn-MOFs with Large Surface Areas

Cited by 25 publications

References 36 publications

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Synthesis of Some Di‐ and Tetraphosphonic Acids by Suzuki Cross‐Coupling

High-Throughput Synthesis of Pillared-Layered Magnesium Tetraphosphonate Coordination Polymers: Framework Interconversions and Proton Conductivity Studies

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From Tetrahedral Tetraphosphonic Acids E[p -C6 H4 P(O)(OH)2 ]4 (E=C, Si) to Porous Cu- and Zn-MOFs with Large Surface Areas

Cited by 25 publications

References 36 publications

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

Synthesis of Some Di‐ and Tetraphosphonic Acids by Suzuki Cross‐Coupling

High-Throughput Synthesis of Pillared-Layered Magnesium Tetraphosphonate Coordination Polymers: Framework Interconversions and Proton Conductivity Studies

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From Tetrahedral Tetraphosphonic Acids E[p -C₆ H₄ P(O)(OH)₂ ]₄ (E=C, Si) to Porous Cu- and Zn-MOFs with Large Surface Areas