Influence of structure-activity relationships on through-space intervalence charge transfer in metal-organic frameworks with cofacial redox-active units
Bowen Ding, Carol Hua, Cameron J Kepert, Deanna M D'Alessandro
CHEMICAL SCIENCE | ROYAL SOC CHEMISTRY | Published : 2019
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 D..View full abstract
The authors gratefully acknowledge the Australian Research Council, the Australian Synchrotron, the Vibrational Spectroscopy Core Facility and Sydney Nano at the University of Sydney for their support of this work. We also thank Associate Professor Brendan Abrahams for assistance in the collection of crystallographic data, Dr Ivan Kassal for discussion on the mobility calculations, and Emeritus Professor Noel Hush for his advice on aspects of the theoretical analysis.