Abstract

The laser-induced fluorescence excitation spectra of zinc phthalocyanine, chloroaluminum phthalocyanine, magnesium phthalocyanine, and free-base phthalocyanine have been investigated under jet-cooled conditions, by using pulsed infrared laser desorption as the means of vaporization. Assignment of the observed vibronic transitions reveals that many of them gain intensity from coupling of theS1(Q) state with theS2(B) andQ′ states. Low-frequency out-of-plane modes of the macrocycle are observed in the region below 100 cm−1; the vibronic structure in this region of the spectrum is sensitive to deviation of the molecule from a planar geometry. TheS1–S0excitation energy shows a weak dependence on the hole size of the macrocycle.

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