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Abstract
A series of phthalonitriles substituted with neopentoxy groups in the 4,5-, 3,6- and 3,4,5,6-positions were synthesized, characterized and subsequently condensed to their corresponding phthalocyanines. The UV-Vis spectrum of the 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecaneopentoxyphthalocyanine was found to be more red shifted than any other hexadecaalkoxy substituted phthalocyanine reported in the literature thus far.
The development of a synthetic method toward the preparation of tetrasubstituted phthalonitriles consisting of amino-alkoxy and amino-thiol substituents is also described. This method involves the reaction of 3,4,5,6-tetrafluorophthaIonitrile with an amine to yield 4,5-diamino-3,6-difluorophthalonitrile. Further reaction of this compound with either, an alcohol or thiol afforded tetra substituted phthalonitriles. Self-condensation of these phthalonitriles was not possible, however, cross condensation reaction of these compounds with phthalonitrile afforded non-centrosymmetric phthalocyanines. In addition, a method for synthesizing a non-centrosymmetric phthalocyanine using monomeric and dimeric phthalocyanine intermediates was examined.
Furthermore, it was discovered that the 1H NMR spectra of the neopentoxy substituted phthalocyanines displayed signs of restricted rotation. Thus, five of the neopentoxy substituted phthalocyanines were subjected to variable temperature 1H NMR studies and their thermokinetic parameters were determined.
