Tuning the Redox Activity of Metal–Organic Frameworks for Enhanced, Selective O2 Binding: Design Rules and Ambient Temperature O2 Chemisorption in a Cobalt–Triazolate Framework

Andrew S. Rosen; M. Rasel Mian; Timur Islamoglu; Haoyuan Chen; Omar K. Farha; Justin M. Notestein; Randall Q. Snurr

doi:10.1021/jacs.9b12401

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

10.26434/chemrxiv.10316681.v1 ◽

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

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 O2 and N2 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-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O2 at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the O2 adsorbate.

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

Inorganic Chemistry ◽

10.1021/acs.inorgchem.0c01124 ◽

2020 ◽

Vol 59 (14) ◽

pp. 9969-9978 ◽

Cited By ~ 1

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

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Combining Organic and Inorganic Redox-Activity: Porphyrin-Based Metal-Organic Frameworks As Electrode Material

ECS Meeting Abstracts ◽

10.1149/ma2019-03/2/142 ◽

2019 ◽

Keyword(s):

Electrode Material ◽

Metal Organic Frameworks ◽

Redox Activity ◽

Metal Organic

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Flexible metal–organic frameworks as superior cathodes for rechargeable sodium-ion batteries

Journal of Materials Chemistry A ◽

10.1039/c5ta03197d ◽

2015 ◽

Vol 3 (32) ◽

pp. 16590-16597 ◽

Cited By ~ 58

Author(s):

Ping Nie ◽

Laifa Shen ◽

Gang Pang ◽

Yaoyao Zhu ◽

Guiyin Xu ◽

...

Keyword(s):

Ambient Temperature ◽

Prussian Blue ◽

Metal Organic Frameworks ◽

Sodium Ion ◽

Sodium Ion Batteries ◽

Prussian Blue Analogues ◽

Ion Storage ◽

Metal Organic ◽

Flexible Metal ◽

Sodium Ion Storage

Flexible metal–organic frameworks composed of Prussian blue analogues on a highly conductive carbonfiber paper have been synthesized and utilized as attractive hosts for sodium ion storage at ambient temperature.

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Hydrogen storage in Co-and Zn-based metal-organic frameworks at ambient temperature

International Journal of Hydrogen Energy ◽

10.1016/j.ijhydene.2009.10.001 ◽

2009 ◽

Vol 34 (24) ◽

pp. 9754-9759 ◽

Cited By ~ 21

Author(s):

Serhiy M. Luzan ◽

Heejin Jung ◽

Hyungphil Chun ◽

A.V. Talyzin

Keyword(s):

Hydrogen Storage ◽

Ambient Temperature ◽

Metal Organic Frameworks ◽

Metal Organic

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Host–Guest Interactions and Redox Activity in Layered Conductive Metal–Organic Frameworks

Chemistry of Materials ◽

10.1021/acs.chemmater.0c01007 ◽

2020 ◽

Vol 32 (18) ◽

pp. 7639-7652

Author(s):

Robert M. Stolz ◽

Akbar Mahdavi-Shakib ◽

Brian G. Frederick ◽

Katherine A. Mirica

Keyword(s):

Metal Organic Frameworks ◽

Redox Activity ◽

Metal Organic

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

Journal of the American Chemical Society ◽

10.1021/jacs.7b03578 ◽

2017 ◽

Vol 139 (23) ◽

pp. 7998-8007 ◽

Cited By ~ 81

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

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Metal Alkoxide Functionalization in Metal−Organic Frameworks for Enhanced Ambient-Temperature Hydrogen Storage

The Journal of Physical Chemistry C ◽

10.1021/jp1094068 ◽

2010 ◽

Vol 115 (5) ◽

pp. 2066-2075 ◽

Cited By ~ 94

Author(s):

Rachel B. Getman ◽

Jacob H. Miller ◽

Kenneth Wang ◽

Randall Q. Snurr

Keyword(s):

Hydrogen Storage ◽

Ambient Temperature ◽

Metal Organic Frameworks ◽

Metal Alkoxide ◽

Metal Organic

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

Magnetochemistry ◽

10.3390/magnetochemistry7080109 ◽

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.

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Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding: Design Rules and Ambient Temperature O2 Chemisorption in a Cobalt−Triazolate Framework

10.26434/chemrxiv.10316681.v2 ◽

2020 ◽

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

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 O2 and N2 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-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predicted that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits weak physisorption of both N2 and O2, whereas the latter is capable of chemisorbing O2 at room temperature in a highly selective manner. The O2 chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the reduced O2 adsorbate.

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