A p-Quinodimethane-Bridged Porphyrin Dimer

• Published in: Chemistry : a European journal 2013-12, Vol.19 (49), p.16814-16824
• Main Authors: Zeng, Wangdong, Ishida, Masatoshi, Lee, Sangsu, Sung, Young Mo, Zeng, Zebing, Ni, Yong, Chi, Chunyan, Kim, Dongho, Wu, Jishan
• Format: Article
• Language: English
• Subjects: Chemistry; chromophores; nearinfrared; polycyclic hydrocarbons; porphyrinoids; quinodimethane
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201302023

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. Fused porphyrin dimer: A p‐quinodimethane‐bridged porphyrin dimer 1 (see figure) has been prepared by an intramolecular Friedel–Crafts alkylation approach. Compound 1 shows intense one‐photon absorption (λmax=955 nm) and a large two‐photon absorption cross‐section (σ(2)max= 2080 GM (at 1800 nm)) in the near‐infrared region.