Fragmentation and slow autoneutralization of isolated negative molecular ions of phthalocyanine and tetraphenylporphyrin

摘要

Macrocyclic tetrapyrrolic compounds, such as naturally occurring or artificial porphyrins and phthalocyanines, have unique and highly attractive properties for applications in medicine and technology. The interaction of free-base phthalocyanine (H2Pc) and tetraphenylporphyrin (H2TPP) molecules with low-energy (0-15 eV) electrons was studied in vacuo by means of negative ion resonant electron capture mass spectrometry. Close similarities in formation and decay of negative ions of these compounds were revealed. Efficient formation of long-lived molecular negative ions (MNIs) was observed in the incident electron energy range of 0-8 eV, unprecedentedly wide for organic compounds and comparable to the range characteristic to carbon atomic clusters, fullerenes. Experiments testify to the strong persistence of MNIs of both compounds to dissociative decay, isomerization, and electron autodetachment. Lifetimes of MNIs as a function of incident electron energy were measured and it was concluded that the isolated anions may retain additional electrons in a time scale of up to hundreds of seconds at standard temperature due to the high adiabatic electron affinity of these large molecules. For the representatives of dyes and photochromic compounds comprehensively studied in terms of interaction with light, the present work highlights yet another unique property of these molecules, namely the capability to attach and durably retain an additional electron of low, pre-ionization energy. Published under license by AIP Publishing.