Synthesis of Crowned Triazolephthalocyanines

Abstract

The synthesis of triazolephthalocyanines bearing crown ether and aza‐crown ether substituents is described. Different substituents have been introduced on the nitrogen atom of the aza‐crown moiety to improve the solubility and the intrinsic amphiphilic character of these macrocycles. The crowned triazolephthalocyanines described have been prepared by a statistical procedure, and also by different variations of a stepwise method. Preliminary studies of the aggregation properties of one representative of this new family of compounds have also been carried out. An exhaustive study of the synthesis of the corresponding dicyano derivative precursors of the triazolephthalocyanines is displayed. Two different approaches have been used for this goal: The first one inserts the cyano groups prior to the synthesis of the crown ether moiety, while the second one builds the crown ether part of the molecule in advance of the cyanation process. The incompatibility of the Rosemund‐von‐Braun cyanation conditions and the presence of nitrogen atoms in the molecule is the main difficulty of the synthesis of these precursors.

Liquid crystalline metal phthalocyanines: Structural organization on the substrate surface

“…The flexible crown macrocycles play a similar role as the long alkyl chains in providing LC properties. Several aza-crown ether-substituted phthalocyanines have been studied [49][50][51][52]. To improve the LC properties, solubility, as well as the amphiphilic character of the compounds various substituents have been attached through the nitrogen atoms of the aza-crown moieties.…”

Liquid crystalline octasubstituted lead(ii) phthalocyanines: effects of alkoxy and alkylthio substituents on film alignment and electrical properties

“…A typical switching effect was also observed in 4a and 4b films with high ON/OFF ratios, making them promising candidates for memory applications. Experimental Materials 4,5-dihydroxyphthalonitrile, 59 4,5-dichlorophthalonitrile, 60 4,5bis(octylthio)phthalonitrile (2a) 61 and 4,5-bis(hexadecylthio) phthalonitrile (2b) 62 were synthesized according to reported procedure. 4,5-bis(octyloxy)phthalonitrile (1a) 31 and 4,5-bis(hexadecyloxy)phthalonitrile (1b) 31 were synthesized according to the modified reported procedure by using 4,5-dihydroxyphthalonitrile as a precursor, which has previously been described by Torres and co-workers.…”

“…4,5-bis(octyloxy)phthalonitrile (1a) 31 and 4,5-bis(hexadecyloxy)phthalonitrile (1b) 31 were synthesized according to the modified reported procedure by using 4,5-dihydroxyphthalonitrile as a precursor, which has previously been described by Torres and co-workers. 59 All other reagents and solvents of reagent-grade quality were obtained from commercial suppliers and were dried as described in Perrin and Armarego. 63…”

Synthesis and Copper(I)‐Driven Disaggregation of a Zinc‐Complexed Phthalocyanine Bearing Four Lateral Coordinating Rings

“…Previous attempts to prepare 4 either by alkylation of 4,5-dicyanocatechol with chloroethoxyethanol [27] or by Pd/C-catalysed hydrogenolysis of bis{2Ј-[2ЈЈ-(benzyloxy)ethoxy]ethoxy}phthalonitrile [28] were unsuccessful. Previous attempts to prepare 4 either by alkylation of 4,5-dicyanocatechol with chloroethoxyethanol [27] or by Pd/C-catalysed hydrogenolysis of bis{2Ј-[2ЈЈ-(benzyloxy)ethoxy]ethoxy}phthalonitrile [28] were unsuccessful.…”