Quadruply Twisted Hückel-Aromatic Dodecaphyrin
Takanori Soya
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorDr. Hirotaka Mori
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorTakanori Soya
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorDr. Hirotaka Mori
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorGraphical Abstract
All in a twist: π-Conjugated macrocycles possessing a quadruply twisted topology were realized by conformational fixation using the insertion of a 1,4-phenylene bridge and PdII metalation. The syn-isomer of bis-PdII complexes displays aromatic character, and is thus identified as the first example of quadruply twisted Hückel aromatic molecule.
Abstract
Molecular topology of π-conjugated circuits becomes increasingly important in the chemistry of aromatic and antiaromatic compounds. meso-Pentafluorophenyl-substituted 5,35-(1,4-phenylene)bridged [56]dodecaphyrin was synthesized by condensation of 1,4-phenylene-bridged dicarbinol dimer and 5,10,15-tris-(pentafluorophenyl)tetrapyrrane followed by oxidation with DDQ and was oxidized to its [54]- and [52]congeners in a stepwise manner. Metalation of the [52]dodecaphyrin with Pd2(dba)3 gave two bis-PdII complexes that are isomers of metalation sites: anti and syn with regard to the 1,4-phenylene bridge. The anti-isomer was easily oxidized to its N-fused form, a quadruply twisted non-aromatic or weakly aromatic macrocycle. On the other hand, the syn-isomer was revealed to be the first example of Hückel aromatic molecule with a quadruply twisted structure.
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- 12aCrystallographic data for 3: C126H36F50N12⋅8(C6H6)⋅2(C6), Mr=3436.66; triclinic; space group P
(No.2), a=14.177(2), b=16.712(4), c=17.278(3) Å; α=106.043(5), β=104.1545(3), γ=97.629(7)°; V=3725.5(12) Å3; ρcalcd=1.174 g cm−3; Z=1; R1=0.0531 [I>2.0σ(I)], wR2=0.1666 (all data), GOF=1.052;
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(No.2), a=19.2854(13), b=28.8466(12), c=30.6271(18) Å; α=108.8038(10), β=108.136(14), γ=103.865(15)°; V=14191(2) Å3; ρcalcd=1.493 g cm−3; Z=2; R1=0.0703 [I>2.0σ(I)], wR2=0.2190 (all data), GOF=1.009;
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