TY - JOUR
T1 - Phthalocyaninodehydroannulenes
AU - Cook, Michael J.
AU - Heeney, Martin J.
N1 - Generated from Scopus record by KAUST IRTS on 2023-02-14
PY - 2000/11/3
Y1 - 2000/11/3
N2 - 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(n) 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.
AB - 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(n) 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.
UR - https://onlinelibrary.wiley.com/doi/10.1002/1521-3765(20001103)6:21%3C3958::AID-CHEM3958%3E3.0.CO;2-Y
UR - http://www.scopus.com/inward/record.url?scp=0034602114&partnerID=8YFLogxK
U2 - 10.1002/1521-3765(20001103)6:21<3958::AID-CHEM3958>3.0.CO;2-Y
DO - 10.1002/1521-3765(20001103)6:21<3958::AID-CHEM3958>3.0.CO;2-Y
M3 - Article
SN - 0947-6539
VL - 6
SP - 3958
EP - 3967
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 21
ER -