Triply Fused ZnII–Porphyrin Oligomers: Synthesis, Properties, and Supramolecular Interactions with Single‐Walled Carbon Nanotubes (SWNTs)

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Abstract
The photophysical, electrochemical, and self‐assembly properties of a novel triply fused ZnII–porphyrin trimer were investigated and compared to the properties of a triply fused porphyrin dimer and the analogous monomer. The trimer exhibited significantly red‐shifted absorption bands relative to the corresponding monomer and dimer. Electrochemical investigations indicated a clear trend in redox properties amongst the three porphyrin structures, with the lowest oxidation potential and the lowest HOMO–LUMO gap exhibited by the triply fused trimer. This electrochemical behavior is attributed to the extensive π‐electron delocalization in the trimeric structure relative to the monomer and dimer. Additionally, it was found that the trimer forms extremely strong and nearly irreversible supramolecular interactions with single‐walled carbon nanotubes (SWNTs), resulting in stable solutions of porphyrin–nanotube complexes in THF. Formation of these complexes required the addition of trifluoroacetic acid (TFA) to the solvent. This allowed the oligomers to make close contact with the nanotubes, enabling the formation of stable supramolecular assemblies. Atomic force microscopy (AFM) was used to observe the supramolecular porphyrin–nanotube complexes and revealed that the porphyrin trimer formed a uniform coating on the SWNTs. Height profiles indicated that nanotube bundles could be exfoliated into either individual tubes or very small bundles by exposure to the porphyrin trimer during sonication.