Peripherally Metalated Secoporphyrazines: A New Generation of Photoactive Pigments

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• 作者：Efstathia G. Sakellariou ; Antonio Garrido Montalban ; Hubert G. Meunier ; Garry Rumbles ; David Phillips ; Richard B. Ostler ; Klaus Suhling ; Anthony G. M. Barrett ; and Brian M. Hoffman
• 刊名：Inorganic Chemistry
• 出版年：2002
• 出版时间：April 22, 2002
• 年：2002
• 卷：41
• 期：8
• 页码：2182 - 2187
• 全文大小：82K
• 年卷期：v.41,no.8(April 22, 2002)
• ISSN：1520-510X

文摘

Base-catalyzed cross condensation of dipropylmaleonitrile 1 with bis(dimethylamino)maleonitrile 2 in an equimolarratio afforded the porphyrazines 3a, 4a, 5a, 6a and 7a. Subsequent demetalation of 5a with TFA followed byremetalation with Zn(OAc)₂ gave ligand 5c in good yield. Compound 5c was, in turn, selectively oxidized andfurther peripherally functionalized using Pt(PhCN)₂Cl₂ and PdCl₂ to yield the novel seco solitaire porphyrazines 10aand 10b. The photophysical profiles of the seco solitaire porphyrazines 10a and 10b were evaluated by means ofabsorption, emission, and transient absorption spectroscopy. The new pigments 10a and 10b were found to bephotochemically more stable than the solitaire complexes 3d and 3e and mediated the generation of singlet oxygenwith quantum yields of 0.59 and 0.45, respectively.