A Semiconductive and Microporous One-Dimensional Tubular Metal-Organic Framework

Ayhan, Mehmet Menaf; Bayraktar, Ceyda; Yu, Kai Bin; Hanna, Gabriel; Yazaydın, A. Özgür; Zorlu, Yunus; Yücesan, Gündoğ

doi:10.26434/chemrxiv.11920026.v1

Cited by 4 publications

(12 citation statements)

References 46 publications

(64 reference statements)

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“…Recently, we reported the first highly stable semiconductive copper-phosphonate MOFs TUB75 and TUB40 with directionally dependent electrical conductivities in the 10 -3 and 10 3 S/m range. [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.…”

Section: Semiconductive Phosphonate Mofsmentioning

confidence: 99%

“…To produce mono-deprotonated phosphonic acid metal-binding groups, we carried out a pH-controlled deprotonation of the Cu-p-H 8 TPPA linker. 34 The four mono-deprotonated phosphonate groups in Cu-p-H 4 TPPA -4 are involved in the formation of the tetrahedral zinc atoms. Each of the zinc atoms is coordinated to a mono-deprotonated phosphonic acid tether of Cu-p-H 4 TPPA -4 , allowing us to achieve the simplest tetrahedral ZnO 4 metal-binding modes and thereby ensuring the extended conjugation of the porphyrin core throughout the MOF.…”

Section: Semiconductive Phosphonate Mofsmentioning

confidence: 99%

“…We adapted the same strategy in this work to reproduce the simplest metal-binding modes observed previously in GTUB4. 34 The Cu(p-H 8 TPPA) linker (see Figure 1a) was synthesized according to our previously reported method (see Figure S3 for the synthetic pipeline). 34 The single crystals of GTUB3 were synthesized in scintillation vials after the reaction of 0.03 mmol Zn(NO 3 ) 2 •6H 2 O, 0.01 mmol Cu-H 8 TPPA, and 1.5 mmol phenylphosphonic acid at 80 °C in the presence of 10 ml:7.5 ml DMF/H 2 O and pH values between 1.7 and 7 (to ensure the mono-deprotonation of the phosphonic acids).…”

Section: Synthesis Of Gtub3mentioning

confidence: 99%

“…34 The Cu(p-H 8 TPPA) linker (see Figure 1a) was synthesized according to our previously reported method (see Figure S3 for the synthetic pipeline). 34 The single crystals of GTUB3 were synthesized in scintillation vials after the reaction of 0.03 mmol Zn(NO 3 ) 2 •6H 2 O, 0.01 mmol Cu-H 8 TPPA, and 1.5 mmol phenylphosphonic acid at 80 °C in the presence of 10 ml:7.5 ml DMF/H 2 O and pH values between 1.7 and 7 (to ensure the mono-deprotonation of the phosphonic acids). The yield of the reaction was 90% and the purity of the crystals was confirmed by EDX elemental analysis (see Figure S4).…”

Section: Synthesis Of Gtub3mentioning

confidence: 99%

“…For example, similar TGA patterns have also been observed in the thermal decomposition profiles of the starting materials Cu(p-H 8 TPPA) and p-H 8 TPPA, and also GTUB4, a nanotubular [Ni(Cu-p-H 4 TPPA)]⋅2 (CH 3 ) 2 NH 2 + MOF (for a comparison, see Figure S5). 34,42…”

Section: Thermal Propertiesmentioning

confidence: 99%

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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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Section: Semiconductive Phosphonate Mofsmentioning

confidence: 99%

Section: Semiconductive Phosphonate Mofsmentioning

confidence: 99%

Section: Synthesis Of Gtub3mentioning

confidence: 99%

Section: Synthesis Of Gtub3mentioning

confidence: 99%

Section: Thermal Propertiesmentioning

confidence: 99%

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

Zorlu¹,

Tholen²,

Ayhan³

et al. 2021

Preprint

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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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Tuning Structural and Optical Properties of Porphyrin‐based Hydrogen‐Bonded Organic Frameworks by Metal Insertion

Tholen

Peeples

Ayhan

et al. 2022

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Herein, a simple way of tuning the optical and structural properties of porphyrin‐based hydrogen‐bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB‐5 (p‐H8‐TPPA (5,10,15,20‐Tetrakis[p‐phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu‐, Ni‐, Pd‐, and Zn‐GTUB‐5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal‐induced structural changes, viz., changes in the metal‐to‐nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu‐, Zn‐, and Pd‐ GTUB‐5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π‐ orbitals on the porphyrin linkers, while that of Ni‐GTUB‐5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal‐insertion can be used to optimize HOFs for optoelectronics and small‐molecule capture applications.

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A Semiconductive and Microporous One-Dimensional Tubular Metal-Organic Framework

Cited by 4 publications

References 46 publications

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

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

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

Tuning Structural and Optical Properties of Porphyrin‐based Hydrogen‐Bonded Organic Frameworks by Metal Insertion

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