A Directly Fused Subporphyrin Dimer with a Wavelike Structure.
[Ni(cod)2 ]-mediated intramolecular reductive coupling of β-β' linked meso,meso'-dibromosubporphyrin dimer gave the anti-isomer of meso-meso', β-β' doubly linked subporphyrin dimer as the first example of a fused subporphyrin dimer. The fused dimer 3anti displays an wavelike coplanar structure, a perturbed and red-shifted absorption spectrum, reversible redox behaviors with a decreased electrochemical HOMO-LUMO band gap, and a short S1 -state lifetime owing to the delocalized π-electronic network.
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8262, Japan.
Yasuhiro
Y
Okuda
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8262, Japan.
Eiji
E
Tsurumaki
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
Juwon
J
Oh
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
Jooyoung
J
Sung
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea. dongho@yonsei.ac.kr.
Dongho
D
Kim
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8262, Japan. osuka@kuchem.kyoto-u.ac.jp.
Atsuhiro
A
Osuka
X-ray diffraction; density functional calculations; dimerization; iridium; porphyrinoids