Influence of structure-activity relationships on through-space intervalence charge transfer in metal-organic frameworks with cofacial redox-active units

Chemical Science
Bowen DingDeanna M D'Alessandro

Abstract

Understanding charge transfer in redox-active metal-organic frameworks (MOFs) is of fundamental importance given the potential of these materials to be used in myriad applications including porous conductors, electrocatalysts and battery materials, amongst others. An important challenge is quantifying the spectroscopic features of these materials in order to elucidate their charge transfer properties. Herein, two topologically related Zn(ii) and Cd(ii) frameworks, [Zn2(DPPTzTz)2(SDC)2] (1-Zn) and [Cd2(DPPTzTz)2(SDC)2] (2-Cd) (where DPPTzTz = 2,5-bis(4-(4-pyridinyl)phenyl)thiazolo[5,4-d]thiazole and SDC = selenophene-2,5-dicarboxylate), incorporating cofacially stacked pairs of redox-active DPPTzTz ligands are presented. The differences in the through-space intervalence charge transfer properties of the mixed-valence forms of the two frameworks generated upon solid state spectroelectrochemical reduction are quantified using Marcus-Hush theory. Further, charge transfer theory is applied to calculate electron mobilities in both extended framework systems. A larger electronic coupling constant, Hab, of 118 cm-1 corresponding to an electron mobility, k, of 6.02 × 108 s-1 was observed for the Zn(ii) analogue compared to the Cd(ii) an...Continue Reading

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Citations

Mar 13, 2019·Chemistry : a European Journal·Jun HeZhengtao Xu
May 28, 2019·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Ryuichi MuraseDeanna M D'Alessandro
Mar 4, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Vadim A DubskikhVladimir P Fedin
Jun 25, 2021·Chemical Science·Bowen DingDeanna M D'Alessandro
Jul 13, 2021·Faraday Discussions·Patrick W DohenyDeanna M D'Alessandro
May 3, 2019·ACS Applied Materials & Interfaces·Xiaobo ShangJoon Hak Oh

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Methods Mentioned

BETA
electron paramagnetic resonance
X-ray

Software Mentioned

Varian Win UV
PLATON
WinGX
Xenon
SQW
SHELXL
SHELXT
SHELXS

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