Specially designed spectroelectrochemical cells were used to record UV-vis absorption and magnetic circular dichroism (MCD) spectral data of the phthalocyanine ring-reduced dianion, [ZnPc(-4)]2-, in situ at room temperature. [ZnPc(-4)]2- was generated at cryogenic temperatures through photoreduction of a vitrified dimethyl formamide/hydrazine hydrate solution using hydrazine as the electron donor. Molecular orbital calculations for [ZnPc(-(2 + n))]-n (n = -1 -4) species were performed through the use of the ZINDO program. The approach that was developed previously to assign the major π → π* and π * → π* transitions in the optical spectrum of [ZnPc(-3)]-, which was based on analysis of the relative signs and intensities of close lying Faraday B terms in the MCD spectrum, is used here to assign the major bands seen in the spectrum of [ZnPc(-4)]2-. The spectrum is dominated by a π* → π* transition out of the partially filled lowest unoccupied molecular orbital (LUMO) which gives rise to a pair of oppositely-signed, coupled B terms in the MCD spectrum at 506 and 620 nm. The Q transition of the phthalocyanine ring is assigned to a weak absorption band at 865 nm, while the second π → π* transition is assigned to a band at 370 nm. The band assignment scheme is extended to data that have been reported previously for more highly ring-reduced main group [MPc(-5)]3- and [MPc(-6)]4- species (M = Mg, Zn). The Q band of [MgPc(-5)]3- is assigned to a band at 1125 nm. Bands at 589 and 825 nm are assigned to π* → π* transitions out of the partially occupied Jahn-Teller split eg* LUMO. The second π → π* transition is assigned to a band at 338 nm. As the LUMO is fully occupied, the spectrum of [MgPc(-6)]4- is dominated by π* → π* bands at 625 and 840 nm. An additional band at 305 nm is assigned to the second π* → π* transition. A general band assignment scheme is proposed for both main group and transition metal phthalocyanine anion species. Stillman@uwo.ca.
|Number of pages||13|
|Publication status||Published - 1997 Dec 1|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry