ABSTRACT
Dissymmetrical α,α'-disubstituted tripyrrins have been prepared using a modified synthetic protocol. Tripyrrin 2a bearing 3,5-bis(trifluoromethyl)phenyl and 4-methoxyphenyl moieties showed an anti-type dimer arrangement in the solid state. In contrast, syn-type dimers were observed for tripyrrin 2b bearing 3,5-bis(trifluoromethyl)phenyl and 3,5-di-t-butylphenyl moieties. In addition, proton-exchange NH tautomerization was observed in 2b.
ABSTRACT
We report here the first rational synthesis of 5,10-diazaporphyrins via nucleophilic substitution reactions of α,α'-dibromotripyrrin. Uses of 1,3-diiminoisoindoline and 3,4-di(ethylsulfanyl)pyrrole-2,5-diimine as nucleophiles allowed for synthesis of 5,10-diazabenzoporphyrin (2) and 5,10-diaza-7,8-di(ethylsulfanyl)porphyrin (3). 3 was reduced to 5,10-diazaporphyrin (4), 5,10-diaza-2,3-dihydrogenated porphyrin (5), and 5,10-diaza-7,8-dihydrogenated porphyrin (6) with yields that were dependent upon reduction conditions. All the structures of these products were confirmed by X-ray crystallographic analysis. Their optical and electrochemical properties have been comparatively studied with those of 5,15-diazaporphyrin (7) and 5,15-diazachlorin (8). Furthermore, NH tautomers of 2 and 4 were observed as different species in solution, and the dynamic NH tautomeric behavior was studied in 4.
ABSTRACT
Double ring expansion from a 5,15-diarylporphyrin to a 5,16-diaryl-10,11,21,22-tetradehydro[20]porphyrin(2.1.2.1) occurred through a reaction sequence consisting of oxidation with PbO2 to 5,15-dioxoporphodimethene, a Corey-Fuchs reaction with tetrabromomethane in the presence of triphenylphosphine, and Fritsch-Buttenberg-Wiechell rearrangement triggered by tert-butyllithium. The obtained tetradehydro[20]porphyrin(2.1.2.1) and its mono- and dihydrogenated congeners exhibited 20 π antiaromatic character, whereas overhydrogenated congeners bearing a saturated bridge were nonaromatic owing to disrupted πâ conjugation.
ABSTRACT
Di-peri-dinaphthoporphyrins can be regarded as a key and common substructure of fused porphyrinoids. PtCl2 -mediated cycloisomerization reaction of quinodimethane-type porphyrins provided these doubly fused porphyrins, which exhibit characteristic paratropic ring currents that presumably arise from 24π antiaromatic circuit as a dominant resonance contributor. UV/Vis absorption spectra, cyclic voltammetry, and excited-state dynamics as well as theoretical calculation support this conclusion.
ABSTRACT
Control of the association behavior by molecular design is one of the most essential benefits in artificial supramolecular systems. 1,14-Dianilinotripyrrin has recently emerged as a novel conjugated molecule which forms a double helix in non-polar solvents with the aid of multiple interstrand hydrogen bonding interactions. In this work, we investigated the substituent effects at the 5,10-positions of tripyrrin on their association thermodynamics. This study illuminated two key findings; 1) electronic tuning by the para-substituents reduce the entropic costs thereby slightly improve the association constants, and 2) ortho-substituents force the tripyrrin core to be relatively planar, which significantly decreases the association constant due to less feasible π-stacking.
Subject(s)
Dimerization , Hydrogen Bonding , Solvents , ThermodynamicsABSTRACT
The dimeric association of α,α'-di(benzylamino)tripyrrin in chloroform was found to be 40 times less effective than that of previously reported α,α'-dianilinotripyrrin, which, however, led us to observe the co-crystal structure of single and double helix forms. Attachment of chiral phenylethylamines on the same tripyrrin platform was also performed to induce helical chirality.
ABSTRACT
As the first example of expanded heteroporphyrins with heteroatoms at meso-positions, 5,20-dithiahexaphyrins and 5,20-diazahexaphyrins were synthesized via nucleophilic substitution reactions of α,α'-dibromotripyrrin as the key step. While 5,20-dithiahexaphyrins are practically nonaromatic, 5,20-[28]diazahexaphyrins show weakly antiaromatic characters and can be cleanly converted into aromatic 5,20-[26]diazahexaphyrins upon oxidation with PbO2, demonstrating distinct aromaticity switching with maintenance of dumbbell-like conformations.
ABSTRACT
A new motif for artificial double helices was developed on the basis of α,α'-disubstituted tripyrrin. α,α'-Dibromotripyrrin 3 was prepared by gentle bromination at the pyrrolic α-positions of 5,10-diphenyltripyrrane followed by oxidation with DDQ. Nucleophilic substitution reactions of 3 with anilines proceeded efficiently to furnish a series of α,α'-dianilinotripyrrins 4-11, which displayed monomeric and dimeric forms depending upon the solvent used for crystallization and the structures of the substituted anilines. Dimeric forms show double helical structures with smooth π-conjugation as indicated by their absorption spectra. van't-Hoff plot analyses revealed that the dimerizations in CDCl3 are enthalpy-driven. Larger association constants of the dimerization are attained for 3,5-di-t-butylanilino- and 3,5-bis(trifluoromethyl)anilino-substituted tripyrrins (7 and 8) via additional multiple intermolecular interactions. In a nonpolar and aprotic solvent, tripyrrins (9 and 10) bearing bulkier 1-naphthylamino and mesitylamino groups do not dimerize but undergo unique tautomerization.