First Synthesis of meso‐Chlorinated Tetrabenzoporphyrins

摘要: meso-Chlorinated bicyclo[2.2.2]octadiene-fused porphyrins 2 (ClnTBCODPs; n = 1–4) have been synthesized by chlorination of the free base TBCODP-H2 (1-H2) using N-chlorosuccinimide (NCS). The chlorinated derivatives were easily separated column chromatography on silica gel to give 2-H2 in good yields. This method for porphyrin NCS is mild, safe, and economic compared with established procedure meso-chlorination porphyrins. We also discovered unexpected dichlorodicyanobenzoquinone (DDQ) single-electron transfer. ClnTBCODPs converted into tetrabenzoporphyrins (ClnTBPs) 3 100 % yields retro-Diels–Alder reaction. derived compounds characterized NMR spectroscopy, UV/Vis spectrophotometry, cyclic voltammetry (CV), X-ray crystallography, organic field-effect transistor (OFET) characteristics. introduction chlorine at meso positions TBPs drastically changed their electronic structural properties. maxima protonated Cl4TBP-H2 (3d-H2; λmax 494, 649, 707 nm) redshifted around 50–65 nm relative those TBP-H2 (λmax 431, 605, 660 nm). two Q-band Cl4TBP dication are similar a tetraacenaphthoporphyrin 525, 646, 702 nm), which has one most Q-bands.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)