Redox-Active Benzoquinones as Challenging “non-innocent” Linkers to Construct 2D Frameworks and Nanostructures with tunable Physical Properties

2022 ◽  
Author(s):  
Noemi N. Monni ◽  
Marco Sanna Angotzi ◽  
Mariangela M. Oggianu ◽  
Suchithra S. Ashoka Sahadevan ◽  
Maria Laura Mercuri
Keyword(s):  
Physical Properties ◽  
Coordination Polymers ◽  
Molecular Level ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Redox Active ◽  
Metal Organic

Exploiting redox activity in supramolecular frameworks such as coordination polymers, metal-organic frameworks and related nanostructures is of paramount importance both at the molecular level and for their technological applications, since...

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.

scholarly journals Exploiting redox activity in metal–organic frameworks: concepts, trends and perspectives

2016 ◽  
Vol 52 (58) ◽  
pp. 8957-8971 ◽  
Author(s):  
D. M. D'Alessandro
Keyword(s):  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Feature Article ◽  
Redox Active ◽  
Active Metal ◽  
Metal Organic ◽  
Redox Active Metal

This feature article highlights latest developments in experimental, theoretical and computational concepts relevant to redox-active metal–organic Frameworks.

Redox-active metal–organic frameworks for energy conversion and storage

2019 ◽  
Vol 7 (28) ◽  
pp. 16571-16597 ◽  
Author(s):  
Joaquín Calbo ◽  
Matthias J. Golomb ◽  
Aron Walsh
Keyword(s):  
Energy Conversion ◽  
Metal Organic Frameworks ◽  
Mixed Valence ◽  
Redox Activity ◽  
Redox Active ◽  
Active Metal ◽  
Energy Conversion And Storage ◽  
Metal Organic ◽  
And Storage ◽  
Redox Active Metal

We review progress in the study of electroactive MOFs with redox activity for energy conversion and storage. Recent advances in mixed-valence MOFs are highlighted, which have led to record conductivities towards metallic porous materials.

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>

Single crystal to single crystal transformation of spin-crossover coordination polymers from 3D frameworks to 2D layers

2021 ◽  
Vol 9 (15) ◽  
pp. 5082-5087
Author(s):  
Yu Gong ◽  
Wang-Kang Han ◽  
Hui-Shu Lu ◽  
Qing-Tao Hu ◽  
Huan Tu ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Single Crystal ◽  
Coordination Polymers ◽  
Ligand Exchange ◽  
Spin Crossover ◽  
Metal Organic Frameworks ◽  
Crystal Transformation ◽  
Metal Organic

New Hofmann-type metal–organic frameworks display rare and complete ligand exchange induced single crystal to single crystal transformations from 3D frameworks to 2D layers, accompanied by magnetic properties transition from two-step SCO behavior to hysteretic SCO behavior.

Synthesis, designing strategies and photocatalytic charge dynamics of Metal-Organic Frameworks (MOFs): A catalyzed Photo-degradation approach towards Organic Dyes

2021 ◽  
Author(s):  
Ayushi Singh ◽  
Ashish Kumar Singh ◽  
Jian-Qiang Liu ◽  
Abhinav Kumar
Keyword(s):  
Small Molecule ◽  
Coordination Polymers ◽  
Organic Dyes ◽  
Metal Organic Frameworks ◽  
Gas Storage ◽  
New Variety ◽  
Photo Degradation ◽  
Charge Dynamics ◽  
Potential Applications ◽  
Metal Organic

Metal-organic frameworks (MOFs) or coordination polymers (CPs) are regarded as new variety of materials that find potential applications in plethora of areas such as gas/small molecule absorption/separation, gas storage, membranes...

scholarly journals Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

Polymers ◽  
2011 ◽  
Vol 3 (4) ◽  
pp. 1750-1775 ◽  
Author(s):  
Anil D. Naik ◽  
Marinela M. Dîrtu ◽  
Antoine P. Railliet ◽  
Jacqueline Marchand-Brynaert ◽  
Yann Garcia
Keyword(s):  
Amino Acid ◽  
Coordination Polymers ◽  
Metal Organic Frameworks ◽  
Metal Organic

Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2uptake, redox-activity and oxygen evolution reaction

2016 ◽  
Vol 45 (16) ◽  
pp. 6901-6908 ◽  
Author(s):  
Barun Dhara ◽  
Subrahmanyam Sappati ◽  
Santosh K. Singh ◽  
Sreekumar Kurungot ◽  
Prasenjit Ghosh ◽  
...  
Keyword(s):  
Physicochemical Properties ◽  
Oxygen Evolution ◽  
Coordination Polymers ◽  
Oxygen Evolution Reaction ◽  
Redox Activity ◽  
Metal Organic

Remarkable differences in the physicochemical properties of metal–organic gels of Fe(iii) and Al(iii) ions with the TCA ligand is reported.

Lanthanide metal–organic frameworks based on the 4,4′-oxybisbenzoic acid ligand: synthesis, structures and physical properties

2015 ◽  
Vol 39 (12) ◽  
pp. 9872-9878 ◽  
Author(s):  
Yun Li ◽  
Ning Wang ◽  
Yan-Ju Xiong ◽  
Qian Cheng ◽  
Jie-Fang Fang ◽  
...  
Keyword(s):  
Physical Properties ◽  
Solvothermal Synthesis ◽  
Metal Organic Frameworks ◽  
Lanthanide Ions ◽  
Acid Ligand ◽  
Metal Organic ◽  
Lanthanide Metal ◽  
Ligand Synthesis

Using solvothermal synthesis, eight new 3D microporous lanthanide-ions-based MOFs constructed from 4,4′-oxybisbenzoic acid were obtained and displayed two types of architecture.

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