Theoretical Investigation of Charge Transfer in Metal
Organic Frameworks for Electrochemical Device Applications
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Abstract
For
electrochemical device applications metal organic frameworks
(MOFs) must exhibit suitable conduction properties. To this end, we
have performed computational studies of intermolecular charge transfer
in MOFs consisting of hexa-Zr<sup>IV</sup> nodes and tetratopic carboxylate
linkers. This includes an examination of the electronic structure
of linkers that are derived from tetraphenyl benzene <b>1</b>, tetraphenyl pyrene <b>2</b>, and tetraphenyl porphyrin <b>3</b> molecules. These results are used to determine charge transfer
propensities in MOFs, within the framework of Marcus theory, including
an analysis of the key parameters (charge transfer integral <i>t</i>, reorganization energy λ, and free energy change
Δ<i>G</i><sup>0</sup>) and evaluation of figures of
merit for charge transfer based on the chemical structures of the
linkers. This qualitative analysis indicates that delocalization of
the HOMO/LUMO on terminal substituents increases <i>t</i> and decreases λ, while weaker binding to counterions decreases
Δ<i>G</i><sup>0</sup>, leading to better charge transfer
propensity. Subsequently, we study hole transfer in the linker <b>2</b> containing MOFs, <b>NU-901</b> and <b>NU-1000</b>, in detail and describe mechanisms (hopping and superexchange) that
may be operative under different electrochemical conditions. Comparisons
with experiment are provided where available. On the basis of the
redox and catalytic activity of nodes and linkers, we propose three
possible schemes for constructing electrochemical devices for catalysis.
We believe that the results of this study will lay the foundation
for future experimental work on this topic