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• W1996363453 abstract "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." @default.
• W1996363453 created "2016-06-24" @default.
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• W1996363453 date "1997-01-01" @default.
• W1996363453 modified "2023-10-02" @default.
• W1996363453 title "Assignment of the Optical Spectra of Metal Phthalocyanine Anions" @default.
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• W1996363453 doi "https://doi.org/10.1021/ic960737i" @default.
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