scholarly journals Spectroelectrochemistry: A Powerful Tool for Studying Fundamental Properties and Emerging Applications of Solid-State Materials Including Metal–Organic Frameworks

2021 ◽  
Vol 74 (2) ◽  
pp. 77
Author(s):  
Deanna M. D'Alessandro ◽  
Pavel M. Usov

Spectroelectrochemistry (SEC) encompasses a broad suite of electroanalytical techniques where electrochemistry is coupled with various spectroscopic methods. This powerful and versatile array of methods is characterised as in situ, where a fundamental property is measured in real time as the redox state is varied through an applied voltage. SEC has a long and rich history and has proved highly valuable for discerning mechanistic aspects of redox reactions that underpin the function of biological, chemical, and physical systems in the solid and solution states, as well as in thin films and even in single molecules. This perspective article highlights the state of the art in solid-state SEC (ultraviolet–visible–near-infrared, infrared, Raman, photoluminescence, electron paramagnetic resonance, and X-ray absorption spectroscopy) relevant to interrogating solid state materials, particularly those in the burgeoning field of metal–organic frameworks (MOFs). Emphasis is on developments in the field over the past 10 years and prospects for application of SEC techniques to probing fundamental aspects of MOFs and MOF-derived materials, along with their emerging applications in next-generation technologies for energy storage and transformation. Along with informing the already expert practitioner of SEC, this article provides some guidance for researchers interested in entering the field.

2021 ◽  
pp. 2102396
Author(s):  
Xianguang Miao ◽  
Peng Wang ◽  
Rui Sun ◽  
Jiafeng Li ◽  
Zhongxiao Wang ◽  
...  

2015 ◽  
Vol 112 (36) ◽  
pp. 11161-11168 ◽  
Author(s):  
Paul R. McGonigal ◽  
Pravas Deria ◽  
Idan Hod ◽  
Peyman Z. Moghadam ◽  
Alyssa-Jennifer Avestro ◽  
...  

The organization of trisradical rotaxanes within the channels of a Zr6-based metal–organic framework (NU-1000) has been achieved postsynthetically by solvent-assisted ligand incorporation. Robust ZrIV–carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. Ultraviolet–visible–near-infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR), and 1H nuclear magnetic resonance (NMR) spectroscopies all confirm the capture of redox-active rotaxanes within the mesoscale hexagonal channels of NU-1000. Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components can be accessed electrochemically in the solid state. In contradistinction to previous methods, this strategy for the incorporation of mechanically interlocked molecules within porous materials circumvents the need for de novo synthesis of a metal–organic framework, making it a particularly convenient approach for the design and creation of solid-state molecular switches and machines. The results presented here provide proof-of-concept for the application of postsynthetic transformations in the integration of dynamic molecular machines with robust porous frameworks.


Author(s):  
Joseph E. Mondloch ◽  
Rachel C. Klet ◽  
Ashlee J. Howarth ◽  
Joseph T. Hupp ◽  
Omar K. Farha

Data in Brief ◽  
2019 ◽  
Vol 25 ◽  
pp. 104280 ◽  
Author(s):  
Aram L. Bugaev ◽  
Alina A. Skorynina ◽  
Elizaveta G. Kamyshova ◽  
Kirill A. Lomachenko ◽  
Alexander A. Guda ◽  
...  

CrystEngComm ◽  
2015 ◽  
Vol 17 (48) ◽  
pp. 9254-9263 ◽  
Author(s):  
Jun He ◽  
Matthias Zeller ◽  
Allen D. Hunter ◽  
Zhengtao Xu

The ever more versatile side groups, from labile weak donors to strong-binding thiol and dendritic functions, sulfur-enabled framework chemistry heralds a rising trend in the design of solid-state materials.


2015 ◽  
Vol 17 (33) ◽  
pp. 21448-21457 ◽  
Author(s):  
Walter S. Drisdell ◽  
Roberta Poloni ◽  
Thomas M. McDonald ◽  
Tod A. Pascal ◽  
Liwen F. Wan ◽  
...  

In situ X-ray absorption spectroscopy, coupled with DFT calculations, uncovers the details of the novel mechanism for CO2 adsorption in diamine-appended metal–organic frameworks.


2017 ◽  
Vol 46 (9) ◽  
pp. 2998-3007 ◽  
Author(s):  
Carol Hua ◽  
Jing-Yuan Ge ◽  
Floriana Tuna ◽  
David Collison ◽  
Jing-Lin Zuo ◽  
...  

Two new Mn2+-based metal–organic frameworks containing the tris(p-tetrazolylphenyl)amine (H3TTPA) ligand exhibit multiple redox-accessible states which have been interrogated using in situ solid state spectroelectrochemical methods.


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