Hypervalent group 15 ions make the porphyrin complexes efficient electron acceptors with highly positive reduction potentials. The inclusion of electron rich substituents on these electron poor porphyrin complexes can induce intramolecular charge transfer (ICT) behavior within the molecule. Herein is examined the ICT behavior resulting from group 15 porphyrin complexes bearing methoxylated phenyl groups in their meso positions. The ICT behavior is evaluated using steady-state and transient spectroscopic techniques accompanied by time-dependent density functional theory calculations. The observed ICT behavior changes as a function of both the position and number of methoxy groups on the phenyl rings, allowing for the properties of the system to be easily tuned for use in various applications. In addition, the ICT behavior of these systems can be switched on and off by modulation of the solvent polarity. The tunable push-pull style electron transfer exhibited by these compounds make them ideal candidates for the construction of supramolecular donor-acceptor systems for solar energy capture and conversion applications.

Tunable intramolecular charge transfer in methoxylated tetraarylporphyrins bearing hypervalent group 15 ions

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