Quantification of the mixed-valence and intervalence charge transfer properties of a cofacial metal-organic framework via single crystal electronic absorption spectroscopy.

Chemical Science
Patrick W DohenyDeanna M D'Alessandro

Abstract

Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal-Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices; however the structure-property relationships pertaining to charge transfer and its quantification are relatively poorly understood. Here, the cofacial Cd(ii)-based MOF [Cd(BPPTzTz)(tdc)]·2DMF (where BPPTzTz = 2,5-bis(4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole, tdc2- = 2,5-thiophene dicarboxylate) exhibits Intervalence Charge Transfer (IVCT) within its three-dimensional structure by virtue of the close, cofacial stacking of its redox-active BPPTzTz ligands. The mixed-valence and IVCT properties are characterised using a combined electrochemical, spectroelectrochemical and computational approach. Single crystal electronic absorption spectroscopy was employed to obtain the solid-state extinction coefficient, enabling the application of Marcus-Hush theory. The electronic coupling constant, Hab, of 145 cm-1 was consistent with the localised mixed-valence properties of both this framework and analogous systems that use alt...Continue Reading

References

Aug 12, 2004·The Journal of Chemical Physics·A Daniel Boese, Jan M L Martin
Sep 29, 2005·Journal of Magnetic Resonance·Stefan Stoll, Arthur Schweiger
May 1, 1948·Journal of the Optical Society of America·P KUBELKA
Jan 28, 2009·Acta Crystallographica. Section D, Biological Crystallography·Anthony L Spek
Oct 18, 2011·Journal of Magnetic Resonance·Paul R MurrayLesley J Yellowlees
Apr 6, 2012·Journal of Applied Crystallography·Christian B HübschleBirger Dittrich
Jul 26, 2012·Journal of the American Chemical Society·Tarun C NarayanMircea Dincă
Dec 20, 2014·Journal of the American Chemical Society·Andrew J CloughSmaranda C Marinescu
Dec 30, 2014·Acta Crystallographica. Section A, Foundations and Advances·George M Sheldrick
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·George M Sheldrick
Oct 13, 2015·Journal of the American Chemical Society·Michael G CampbellMircea Dincă
Mar 19, 2016·Chemical Communications : Chem Comm·D M D'Alessandro
Feb 24, 2017·Journal of the American Chemical Society·Jordan A DeGaynerT David Harris
Nov 8, 2017·Chemical Society Reviews·Guillermo Mínguez Espallargas, Eugenio Coronado
Feb 10, 2018·Journal of the American Chemical Society·Ben A JohnsonSascha Ott
May 5, 2018·Journal of the American Chemical Society·Carol HuaDeanna M D'Alessandro
May 29, 2018·Chemical Communications : Chem Comm·Shaoyang LinAmanda J Morris
Jul 7, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Lei SunMircea Dincă
Dec 12, 2018·Chemical Communications : Chem Comm·Marilyn Esclance DMelloSuresh Babu Kalidindi
May 28, 2019·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Ryuichi MuraseDeanna M D'Alessandro

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Citations

Jun 25, 2021·Chemical Science·Bowen DingDeanna M D'Alessandro
Jul 13, 2021·Faraday Discussions·Patrick W DohenyDeanna M D'Alessandro

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Methods Mentioned

BETA
light scattering
single crystal spectroscopy
X-ray

Software Mentioned

PLATON
SHELXL
Easyspin
SHELXT
Gaussian

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