A p-quinodimethane-bridged porphyrin dimer

Wangdong Zeng, Masatoshi Ishida, Sangsu Lee, Young Mo Sung, Zebing Zeng, Yong Ni, Chunyan Chi, Dongho Kim, Jishan Wu

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Abstract

A p-quinodimethane (p-QDM)-bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross-conjugated keto-linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel-Crafts alkylation of the diol-linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one-photon absorption (OPA, λmax=955 nm, ε=45400 M-1 cm-1) and a large two-photon absorption (TPA) cross-section (σ(2) max=2080 GM at 1800 nm) in the near-infrared (NIR) region due to its extended π-conjugation and quinoidal character. It also exhibits a short singlet excited-state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground-state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto-linked dimer 8 b. This research has revealed that incorporation of a p-QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.

Original languageEnglish
Pages (from-to)16814-16824
Number of pages11
JournalChemistry - A European Journal
Volume19
Issue number49
DOIs
Publication statusPublished - 2013 Dec 2

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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    Zeng, W., Ishida, M., Lee, S., Sung, Y. M., Zeng, Z., Ni, Y., Chi, C., Kim, D., & Wu, J. (2013). A p-quinodimethane-bridged porphyrin dimer. Chemistry - A European Journal, 19(49), 16814-16824. https://doi.org/10.1002/chem.201302023