TY - JOUR
T1 - Cation- or Solvent-Induced Supermolecular Phthalocyanine Formation
T2 - Crown Ether Substituted Phthalocyanines
AU - Kobayashi, Nagao
AU - Lever, A. B.P.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1987/11/1
Y1 - 1987/11/1
N2 - Phthalocyanines with four 15-crown-5 ether voids at the 3,4-positions (MtCRPc) (Mt = H2, Zn, Co, Ni, Cu) have been synthesized and characterized. Dimerization of MtCRPc is induced in solvents such as methanol and by addition of some cations (K+, Ca2+, NH4+), especially K+> Cofacial dimer formation in the presence of these cations proceeds in a two-step three-stage process, as indicated by absorption and emission spectroscopy. These species have a highly specific DAh eclipsed configuration providing well-defined dimeric species for spectroscopic analysis. The ESR spectrum of the cation-induced dimeric CuCRPc shows axial symmetry and may be analyzed in terms of an interplanar separation of 4.1 A. The 1H NMR spectra of the cation-induced metal-free and zinc dimers are consistent with an eclipsed configuration. Upper excited state (Soret, S2) emission is observed for the first time in the phthalocyanine series.
AB - Phthalocyanines with four 15-crown-5 ether voids at the 3,4-positions (MtCRPc) (Mt = H2, Zn, Co, Ni, Cu) have been synthesized and characterized. Dimerization of MtCRPc is induced in solvents such as methanol and by addition of some cations (K+, Ca2+, NH4+), especially K+> Cofacial dimer formation in the presence of these cations proceeds in a two-step three-stage process, as indicated by absorption and emission spectroscopy. These species have a highly specific DAh eclipsed configuration providing well-defined dimeric species for spectroscopic analysis. The ESR spectrum of the cation-induced dimeric CuCRPc shows axial symmetry and may be analyzed in terms of an interplanar separation of 4.1 A. The 1H NMR spectra of the cation-induced metal-free and zinc dimers are consistent with an eclipsed configuration. Upper excited state (Soret, S2) emission is observed for the first time in the phthalocyanine series.
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U2 - 10.1021/ja00258a030
DO - 10.1021/ja00258a030
M3 - Article
AN - SCOPUS:33845282967
VL - 109
SP - 7433
EP - 7441
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 24
ER -