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

Research output: Contribution to journalArticle

29 Citations (Scopus)

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 - Dec 2 2013

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Porphyrins
Dimers
Photons
Optical properties
Infrared radiation
Addition reactions
Alkylation
Chromophores
Excited states
Electronic properties
Ground state
Electronic structure
Density functional theory
Energy gap
Display devices
Oxidation
Geometry
Air

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

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

A p-quinodimethane-bridged porphyrin dimer. / Zeng, Wangdong; Ishida, Masatoshi; Lee, Sangsu; Sung, Young Mo; Zeng, Zebing; Ni, Yong; Chi, Chunyan; Kim, Dongho; Wu, Jishan.

In: Chemistry - A European Journal, Vol. 19, No. 49, 02.12.2013, p. 16814-16824.

Research output: Contribution to journalArticle

Zeng, W, Ishida, M, Lee, S, Sung, YM, Zeng, Z, Ni, Y, Chi, C, Kim, D & Wu, J 2013, 'A p-quinodimethane-bridged porphyrin dimer', Chemistry - A European Journal, vol. 19, no. 49, pp. 16814-16824. https://doi.org/10.1002/chem.201302023
Zeng, Wangdong ; Ishida, Masatoshi ; Lee, Sangsu ; Sung, Young Mo ; Zeng, Zebing ; Ni, Yong ; Chi, Chunyan ; Kim, Dongho ; Wu, Jishan. / A p-quinodimethane-bridged porphyrin dimer. In: Chemistry - A European Journal. 2013 ; Vol. 19, No. 49. pp. 16814-16824.
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