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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 25, Number 2
BKCSDE 25(2)
February 20, 2004 

Self-Assembled and Alternative Porphyrin-Phthalocyanine Array
Gwanghoon Kwag*, Eunjoo Park, Sunghyun Kim*
1-Dimensional porphyrin-phthalocyanine array, XANES
An alternative molecular porphyrin-phthalocyanine aggregate was prepared and characterized with UV-visible and X-ray absorption spectroscopies. UV-visible experiments evidence 1-dimensional porphyrin-phthalocyanine array formed by mixing SnTPPCl2 ( λmax = 429, ε = 2.4 × 105/M·cm) and NiPc(OBu)8 ( λmax = 744 nm, ε = 2.0 × 105/M·cm) in solution. In the UV-visible spectrum of the porphyrin-phthalocyanine array, (SnPNiPc)n, a new Q-band appeared at 844 nm with decrease of the Q-band peak of NiPc(OBu)8 at 744 nm. The red-shift of Q-band evidences an alternative porphyrin-phthalocyanine array formed in solution through metal-halide interaction rather than π- π facial interaction, in which nickel of NiPc(OBu)8 coordinates with chloride of SnTPPCl2 through self assembly. Ni K-edge XANES (X-ray absorption near edge structure) spectra also support the axial ligation of nickel to chloride. The square planar structure of NiPc(OBu)8 turns to an octahedral structure in (SnPNiPcSnP) by axial ligation. A higher energy-shift (0.2 eV) of the preedge peak of (SnPNiPcSnP) indicates partial oxidation of nickel by charge transfer from NiPc(OBu)8 to SnTPPCl2.
298 - 300
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