Tetrakis(thiadiazole)porphyrazines. 6. Spectroelectrochemical and Density Functional Theory Studies of the Anions [TTDPzM]n− (n = 1−4; M = ZnII, Mg

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• 作者：Maria Pia Donzello ; Claudio Ercolani ; Xiaohui Cai ; Karl M. Kadish ; Giampaolo Ricciardi ; Angela Rosa
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：October 19, 2009
• 年：2009
• 卷：48
• 期：20
• 页码：9890-9903
• 全文大小：1224K
• 年卷期：v.48,no.20(October 19, 2009)
• ISSN：1520-510X

文摘

Following previous cyclic voltammetric studies of tetrakis(thiadiazole)porphyrazines [TTDPzM] where M = Zn^II, Mg^II(H₂O), Cu^II, or 2H^I in nonaqueous media, a thin-layer spectroelectrochemical investigation was carried out in pyridine to characterize each stepwise one-electron reduction of the electrogenerated [TTDPzM]ⁿ⁻ complexes where n = 1−4. A similar UV−visible spectrum was observed for each form of the anion, independent of the central metal ion and detailed theoretical calculations by density functional theory (DFT) and time-dependent DFT (TDDFT) methods were applied to interpret the spectral features of [TTDPzZn]ⁿ⁻ (n = 1−4) which was selected as representative for describing the ground and excited-state electronic structures of the entire [TTDPzM]ⁿ⁻ series. The use of two exchange-correlation functionals, the pure, asymptotically correct statistical average of orbital potentials (SAOP) and the hybrid B3LYP functionals, proved to be essential for attaining a correct assignment of the key spectral features. The nature and intensity of the main spectral features are highlighted and interpreted on the basis of the ground-state electronic structure of the complexes.