Porphyrin-stabilized meso- or β-carbocations were generated upon treatment of the corresponding bis(4-tert-butylphenyl)porphyrinylcarbinols with trifluoroacetic acid (TFA). Bis(4-tert-butylphenyl)porphyrinylcarbinols were treated with TFA to generate the corresponding carbocations stabilized by a meso- or β-porphyrinyl group. The meso-porphyrinylmethyl carbocation displayed more effective charge delocalization with decreasing aromaticity compared with the β-porphyrinylmethyl carbocation. A propeller-like porphyrin trimer, tris(β-porphyrinyl)carbinol, was also synthesized and converted to the corresponding cation that displayed a more intensified absorption reaching over the NIR region. meso-Porphyrinylmethyl carbanion was generated as a stable species upon deprotonation of bis(4-tert-butylphenyl)(meso-porphyrinyl)methane with potassium bis(trimethylsilyl)amide (KHMDS) and crown-6, whereas β-porphyrinylmethyl anions were highly unstable.
Bibliographical noteFunding Information:
The authors thank Prof. Dr. H. Maeda and Dr. Y. Bando (Ritsumeikan University) for MALDI-TOF-MS measurements. H.Y. thanks the Kansai Research Foundation for Technology Promotion and The Asahi Glass Foundation for financial support. The research at Yonsei University was supported by the Global Research Laboratory (GRL) Program (2013K1A1A2A02050183) of the Ministry of Education, Science and Technology (MEST) of Korea.
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All Science Journal Classification (ASJC) codes
- Organic Chemistry