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Phthalocyaninodehydroannulenes
Author(s) -
Cook Michael J.,
Heeney Martin J.
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20001103)6:21<3958::aid-chem3958>3.0.co;2-y
Subject(s) - phthalocyanine , chemistry , sonogashira coupling , stille reaction , trimer , photochemistry , porphyrin , nickel , cyanine , bromine , mass spectrometry , bathochromic shift , alkoxy group , crystallography , medicinal chemistry , organic chemistry , palladium , catalysis , dimer , chromatography , fluorescence , alkyl , physics , quantum mechanics
4‐Bromo‐ and 4,5‐dibromo‐3,6‐dibutoxyphthalonitrile have been prepared and treated with 3,6‐didecylphthalonitrile in cross tetramerisation reactions in the presence of nickel acetate to afford monobromo‐ and dibromo‐dibutoxyhexadecylphthalocyaninato nickel( II ) complexes. Sonogashira and Stille coupling reactions on these compounds displaced the bromine substituents by ethynyl groups. Oxidative coupling of the monoethynyl derivatised nickel phthalocyanine afforded a butadiynyl‐linked dinuclear phthalocyanine. The corresponding coupling reaction of the diethynylated phthalocyanine gave a mixture of phthalocyaninodehydroannulenes. Separation of the mixture yielded the diphthalocyaninodehydro[12]annulene as the major product. Electrospray mass spectrometry provides evidence for its aggregation in solution. The corresponding cyclic trimer, the triphthalocyaninodehydro[18]annulene, has been identified as a minor product. Both compounds show a large splitting of the Q‐band absorption in the visible region spectrum. Most of the mononuclear phthalocyanine precursors exhibit discotic liquid crystal behaviour. The diphthalocyaninodehydro[12]annulene also enters a mobile phase on heating, but undergoes an irreversible change at 220 °C. MALDI‐TOF mass spectrometry of the product reveals that the compound undergoes oligomerisation at this temperature.