Reversible Redox Activity in Multicomponent Metal–Organic Frameworks Constructed from Trinuclear Copper Pyrazolate Building Blocks

2017 ◽  
Vol 139 (23) ◽  
pp. 7998-8007 ◽  
Author(s):  
Binbin Tu ◽  
Qingqing Pang ◽  
Huoshu Xu ◽  
Xiaomin Li ◽  
Yulin Wang ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Redox Activity ◽  
Reversible Redox ◽  
Metal Organic

scholarly journals Redox Activity as a Powerful Strategy to Tune Magnetic and/or Conducting Properties in Benzoquinone-Based Metal-Organic Frameworks

2021 ◽  
Vol 7 (8) ◽  
pp. 109
Author(s):  
Noemi Monni ◽  
Mariangela Oggianu ◽  
Suchithra Ashoka Sahadevan ◽  
Maria Laura Mercuri
Keyword(s):  
Electrode Materials ◽  
Metal Organic Frameworks ◽  
Future Generation ◽  
Building Blocks ◽  
Redox Activity ◽  
Semiquinone Radical ◽  
Molecular Building Blocks ◽  
Redox Active ◽  
Metal Organic ◽  
Selection Of

Multifunctional molecular materials have attracted material scientists for several years as they are promising materials for the future generation of electronic devices. Careful selection of their molecular building blocks allows for the combination and/or even interplay of different physical properties in the same crystal lattice. Incorporation of redox activity in these networks is one of the most appealing and recent synthetic strategies used to enhance magnetic and/or conducting and/or optical properties. Quinone derivatives are excellent redox-active linkers, widely used for various applications such as electrode materials, flow batteries, pseudo-capacitors, etc. Quinones undergo a reversible two-electron redox reaction to form hydroquinone dianions via intermediate semiquinone radical formation. Moreover, the possibility to functionalize the six-membered ring of the quinone by various substituents/functional groups make them excellent molecular building blocks for the construction of multifunctional tunable metal-organic frameworks (MOFs). An overview of the recent advances on benzoquinone-based MOFs, with a particular focus on key examples where magnetic and/or conducting properties are tuned/switched, even simultaneously, by playing with redox activity, is herein envisioned.

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

2019 ◽  
Author(s):  
Andrew Rosen ◽  
M. Rasel Mian ◽  
Timur Islamoglu ◽  
Haoyuan Chen ◽  
Omar Farha ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Screening Methods ◽  
Bridging Ligands ◽  
Metal Centers ◽  
Computational Screening ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O<sub>2</sub> and N<sub>2</sub> adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

Four metal–organic frameworks built from distinct secondary building blocks: Syntheses, structures, photoluminescence and photocatalytical properties

Polyhedron ◽  
2014 ◽  
Vol 70 ◽  
pp. 180-187 ◽  
Author(s):  
Peng Du ◽  
Yan Yang ◽  
Ying-Ying Liu ◽  
Yuan-Chun He ◽  
Hong-Mei Zhang ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Metal Organic

A Molecular Artisans Guide to Supramolecular Coordination Complexes and Metal Organic Frameworks

2015 ◽  
Vol 03 (01n02) ◽  
pp. 1540004 ◽  
Author(s):  
Xialu Wu ◽  
David J. Young ◽  
T. S. Andy Hor
Keyword(s):  
Chemical Reactivity ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Coordination Complexes ◽  
Large Molecules ◽  
Molecular Building Blocks ◽  
Supramolecular Coordination ◽  
Metal Organic ◽  
Molecular Synthesis ◽  
And Function

As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.

Supermolecular Building Blocks (SBBs) for the Design and Synthesis of Highly Porous Metal-Organic Frameworks

2008 ◽  
Vol 130 (6) ◽  
pp. 1833-1835 ◽  
Author(s):  
Farid Nouar ◽  
Jarrod F. Eubank ◽  
Till Bousquet ◽  
Lukasz Wojtas ◽  
Michael J. Zaworotko ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Porous Metal ◽  
Building Blocks ◽  
Design And Synthesis ◽  
Metal Organic ◽  
Highly Porous

scholarly journals In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

Polymorphous Indium Metal–Organic Frameworks Based on a Ferrocene Linker: Redox Activity, Porosity, and Structural Diversity

2020 ◽  
Vol 59 (14) ◽  
pp. 9969-9978 ◽  
Author(s):  
Jannik Benecke ◽  
Erik Svensson Grape ◽  
Alexander Fuß ◽  
Stephan Wöhlbrandt ◽  
Tobias A. Engesser ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Structural Diversity ◽  
Redox Activity ◽  
Metal Organic ◽  
Indium Metal

Novel Metal-Organic Frameworks Incorporating [Cp°2Mo2P4S] (Cp° = 1-tBu-3,4-Me2C5H2), P4S3 and Cu2I2 Building Blocks (Eur. J. Inorg. Chem. 6/2011)

2011 ◽  
Vol 2011 (6) ◽  
pp. n/a-n/a
Author(s):  
Christian Gröger ◽  
Hans Robert Kalbitzer ◽  
Michael Pronold ◽  
Dmitry Piryazev ◽  
Manfred Scheer ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Metal Organic

3D Metal−Organic Frameworks Based on Elongated Tetracarboxylate Building Blocks for Hydrogen Storage

2008 ◽  
Vol 47 (10) ◽  
pp. 3955-3957 ◽  
Author(s):  
Liqing Ma ◽  
Jeong Yong Lee ◽  
Jing Li ◽  
Wenbin Lin
Keyword(s):  
Hydrogen Storage ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Metal Organic
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