Design and synthesis of near-infrared absorbing pigments. II. Structure determination of aceanthrene green and derivatives

Abstract

Abstract:The reported structure of aceanthrene green, a pigment prepared by potassium hydroxide fusion of 1.9-anthracenedicarboxylic imide, was found to be incorrect. The structure of the pigment is reassigned to 7,8,15,16-dibenzo[a j]perylenetetracarboxylic diimide on the basis of COSY, NOESY, and inversion-recovery 'H NMR experiments. N-Alkyl-or N-phenyl-l,9-anthracenedicarboxylic imides, aceanthryleno[l,2-blquinoxaline, and a benzimidazole derivative of 1,9-anthracenedicarboxylic anhydride were found to give the same dibenzo[a jlperylene structure when reacted in potassium hydroxide. The electronic spectra of these derivatives is reported and it is shown that, as predicted by Pariser-Parr-Pople calculations, they absorb in the near-infrared. Finally, a mechanistic outline for the fusion is proposed on the basis of AM1 and frontier molecular orbital calculations.Key words: photoconductor, near-infrared, aceanthrene green, alkalifusion, polycyclic aromatic hydrocarbon.RCsumC : On a trouvC que la structure proposCe anterieurement pour l'ackanthrbne vert, un pigment prCparC par fusion de l'imide de l'acide anthracbne-l,9-dicarboxylique avec de l'hydroxyde de potassium, est incorrecte. En se basant sur des expkriences COSY, NOESY et d'inversion-rCcupCration en RMN du 'H on lui a rCattribuC la structure du diimide de l'acide dibenzo[a jlpCrylbne-7,8,15,16-tCtracarboxylique. On a trouvC que par rCaction, par fusion avec de l'hydroxyde de potassium, les N-alkyl-ou N-phCnylimides de l'acide anthrackne-1,9-di-carboxylique, l'acCanthrylCno[l,2-b]quinoxaline et un dCrivC benzimidazole de l'anhydride de l'acide anthracbne-l,9-dicarboxylique conduisent tous B la m&me structure dibenzo[a jlpCrylkne. On rapporte les spectres Clectroniques de ces dCrivCs et il est montrC, tel que prCdit par des calculs de type Pariser-Parr-Pople, qu'ils absorbent dans le proche infrarouge. Enfin, en se basant sur des calculs d'orbitales molCculaires AM1 et frontibres, on propose un aperp du mCcanisme pour la fusion.Mots cles : photoconducteur, proche infrarouge, acCanthrbne vert, fusion alcaline, hydrocarbure polycyclique aromatique.[Traduit par la rCdaction]

Anthracene Carboxyimides and Their Dimers

“…This ratio is higher than that reported in a previous investigation in which 6 a was the starting material. [15] Only 7 was detected in the reaction of N-alkylated or N-arylated derivatives of 6 with the alkali melt (monitored by TLC and NMR spectroscopy), in accordance with the earlier investigation. [15] .…”

“…[15] Only 7 was detected in the reaction of N-alkylated or N-arylated derivatives of 6 with the alkali melt (monitored by TLC and NMR spectroscopy), in accordance with the earlier investigation. [15] . The alkali-induced coupling of 6 results first in the formation of a red vat of the green vat dye 7 and is thus completely different from the formation of other carboxyimides, such as perylenetetracarboxydiimides.…”

“…The amidine from 3 and 1,2-phenylenediamine has already been reported as a maroon powder with a melting point of 234 8C. [15] A second bright-orange modification of 13 was also found with a melting point of 228 8C and a pronounced solid-state fluorescence. Both modifications can be interconverted by crystallisation.…”

Novel Core‐Expanded Rylenebis(Dicarboximide) Dyes Bearing Pentacene Units: Facile Synthesis and Photophysical Properties

“…The hexabromide 10 possesses an enhanced solubility relative to 1 c, but a lower photochemical stability. It was found that only bromides closest to the imide positions (1,6,11,16) were substituted with the phenoxy groups upon phenoxylation. The two "inner" bromides remained even after the long reaction times and drastic conditions.…”

“…Benzannulation in the "bay"-region of rylenes with the introduction of anthracene (2, l max = 701 nm) or tetracene (3, l max = 1018 nm) elements resulted in significant bathochromic shifts of the absorption maximum, presumably due to the nonplanarity of the molecules formed. [11][12][13] The absorption of dibenzoperylenebis(dicarboximide) [11] 2 and dibenzopentarylenebis(dicarboximide) [13] 3 was shifted by about 180 nm relative to the perylene 1 a (l max = 524 nm) and pentarylene 1 d (l max = 830 nm) derivatives, respectively. [10] However, enlargement of the p system did not always promote a shift to longer wavelengths.…”