Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers

Assi, Hala Abou; Pérez, Laura C. Pardo; Mouchaham, Georges; Ragon, Florence; Nasalevich, Maxim A.; Guillou, Nathalie; Martineau, Charlotte; Chevreau, Hubert; Kapteijn, Freek; Gascón, Jorge; Fertey, Pierre; Elkaı̈m, Erik; Serre, Christian; Devic, Thomas

doi:10.1021/acs.inorgchem.6b01060

Cited by 73 publications

(70 citation statements)

References 59 publications

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“…In the solid‐state 13 C cross‐polarization under magic‐angle spinning (CPMAS) NMR spectrum of MIP‐205 (Figure ), the resonances of these disordered free acid groups were observed above 170 ppm (see SI for spectrum assignment). Analysis of the multiple‐contact CP (MC‐CP) NMR spectrum (see SI), which provides quantitative information in MOFs, is consistent with the presence of one free acetic acid moiety per linker. Note that the connection of the linker to the Zr 4+ cations strongly affects the chemical shifts of the two allyl carbons ( ca 4 ppm shift between the pure and connected linker, Figure ).…”

Section: Resultsmentioning

confidence: 70%

A Microporous Zirconium Metal‐Organic Framework Based on trans‐Aconitic Acid for Selective Carbon Dioxide Adsorption

et al. 2019

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The discovery of naturally occurring linker-based zirconium MOFs with permanent porosity and accessible functional groups remains a challenge. Using trans-aconitic acid to assemble with Zr 6 oxoclusters under green and scalable conditions, a novel microporous Zr-aconitate framework has been prepared successfully with a high space-time yield. This MOF is isostructural to the previously reported Zr-fumarate, however with a smaller pore size and an abundant concentration of free IntroductionZirconium metal-organic frameworks (MOFs) have been intensively investigated and developed over the last decade, mainly due to their improved stability compared to most of the other metal cations-based MOFs. [1] Among diverse organic linkers used for Zr-MOFs, the majority are artificially synthetic ones, including most of the aromatic multi-carboxylic acids, [2] phenolates [3] and phosphonates. [4] In sharp contrast to artificial linkers, naturally occurring ones display numerous advantages, such as low toxicity and bio-compatibility, cost-effective, easy and abundant availability, which fulfil the sustainable development criteria. Nevertheless, there are very limited examples of Zr-MOFs constructed from naturally occurring linkers. Indeed only the three-dimensional (3D) Zr-Fumarate (also known as MOF-801) [5] and 2D Zr-formate, [6] have been reported so far. The 3D Zr-Fumarate is of particular interest due to its UiO-66 type rigid micropore system. [7] It was reported as a promising material in applications including water harvesting [8] and removal of fluoride contaminant. [9] The incorporation of functional groups into [a]

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Section: Resultsmentioning

confidence: 70%

A Microporous Zirconium Metal‐Organic Framework Based on trans‐Aconitic Acid for Selective Carbon Dioxide Adsorption

et al. 2019

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“…However, the presence of –COO − groups remains essential in order to ensure a very low solubility of the organic material in the carbonate-based liquid electrolyte 9 , 15 , 47 , 51 , 54 – 57 . Figure 1c illustrates the chelating bonding mode between the organic tetraanion and the countercations (while maintaining Li + on the phenolates), based on crystallographic data reported for metal organic frameworks (MOFs) using p -DHT as polytopic linker 58 , 59 . The nature and position of the metal has an influence on the M–O bonds, and this effect is transferred to the C–O bonds causing changes in the electronic distribution in the ligand.…”

Section: Resultsmentioning

confidence: 99%

Raising the redox potential in carboxyphenolate-based positive organic materials via cation substitution

et al. 2018

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Meeting the ever-growing demand for electrical storage devices requires both superior and “greener” battery technologies. Nearly 40 years after the discovery of conductive polymers, long cycling stability in lithium organic batteries has now been achieved. However, the synthesis of high-voltage lithiated organic cathode materials is rather challenging, so very few examples of all-organic lithium-ion cells currently exist. Herein, we present an inventive chemical approach leading to a significant increase of the redox potential of lithiated organic electrode materials. This is achieved by tuning the electronic effects in the redox-active organic skeleton thanks to the permanent presence of a spectator cation in the host structure exhibiting a high ionic potential (or electronegativity). Thus, substituting magnesium (2,5-dilithium-oxy)-terephthalate for lithium (2,5-dilithium-oxy)-terephthalate enables a voltage gain of nearly +800 mV. This compound being also able to act as negative electrode via the carboxylate functional groups, an all-organic symmetric lithium-ion cell exhibiting an output voltage of 2.5 V is demonstrated.

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“…Crystalline coordination polymers based on Ti and hydroxycarboxylate ligands have also been documented. For example, the reaction of Ti 4+ and 2,5‐dihydroxyterephthalic acid under different conditions leads to the isolation of NTU‐9 (NTU stands for Nanyang Technological University), MIL‐167, MIL‐168, and MIL‐169 . Among them, NTU‐9 shows a large hexagonal cavity with a diameter of 11 Å, although the permanent porosity has not been assessed.…”

Section: Stable Metal–organic Frameworkmentioning

confidence: 99%

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

et al. 2018

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Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

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Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers

Cited by 73 publications

References 59 publications

A Microporous Zirconium Metal‐Organic Framework Based on trans‐Aconitic Acid for Selective Carbon Dioxide Adsorption

A Microporous Zirconium Metal‐Organic Framework Based on trans‐Aconitic Acid for Selective Carbon Dioxide Adsorption

Raising the redox potential in carboxyphenolate-based positive organic materials via cation substitution

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

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