Synthesis and Structure of 16 π Octaalkyltetraphenylporphyrins

Abstract

The oxidized octaethyltetraphenylporphyrin (1, OETPP) and the corresponding newly prepared octaisobutyltetraphenylporphyrin (3, OisoBuTPP) could be isolated from the reaction of OETPPLi2 (or OisoBuTPPLi2) with SOCl2. The X-ray analysis and the characteristic UV-vis spectra of 1 and 3 revealed that these are the first examples of 16 pi nonaromatic porphyrins.

Synthesis and characterization of the most distorted 16π porphyrin: 16π octaisopropyltetraphenylporphyrin (OiPTPP)

“…X-ray structural analysis revealed that this novel species is the most distorted known 16π porphyrin, in agreement with our working hypothesis. The reaction of 16π OiPTPP with LiBF 4 followed by Pd 2 (dba) 3 afforded the corresponding 18π OiPTPP palladium(II) complex. X-ray analysis revealed that this complex was highly distorted compared with its 18π OiBTPP palladium(II) complex counterpart.…”

“…While these types of porphyrinoids have been intensively studied, investigations on ordinary porphyrins with [4n]π core electrons are rare and the chemistry of this group of porphyrins is still in the stage of development due to their synthetic difficulty and unstable nature. Whereas several examples of the doubly reduced species (20 π-electron state) have been characterized [2], the doubly oxidized species (16 π-electron state) have been reported only recently, by us [3] and Vaid's group [4] (Fig. 1).…”

The CH/π Hydrogen Bond: Implication in Crystal Engineering

“…Other recent examples showing CH/π hydrogen bonds in clathrates are a CH 2 Cl 2 complex of a porphyrin derivative [104], a CH 3 CN complex of a metallomacrocyle [105], an ethyne complex of a benzoyltricamphor derivative [106], a dicyclopentadienylaluminum complex [107], tetraarylpyrenes [108], 3-amino-2-(4-dimethylaminophenyldiazenyl)-1-phenylbut-2-en-1-one [109], iron and nickel complexes of 4-p-tolyl-2,6-di(2-pyrazinyl)pyridine [110], [Cu 2 (4,4 -bpy) 5 [111], copper complexes with pyrazolylpyrimidines as ligands [112], and host-guest complexes of cucurbit [8]uril [113]. Toda wrote excellent reviews on this issue [114].…”

Pyrrole‐Bridged Porphyrin Nanorings

“…In recent years, the chemistry of isophlorins has been reactivated in light of its relevance to antiaromatic porphyrins. [12][13][14] Synthesis of pyrrole-bridged porphyrin rings 3 H-5 H is straightforward through Suzuki-Miyaura cross-coupling of 5,10-diaryl-15,20-dibromoporphyrin 1…”