Design and Synthesis of Porphyrin-Based Optoelectronic Gates

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• 作者：Arounaguiry Ambroise ; Richard W. Wagner ; Polisetti Dharma Rao ; Jennifer A. Riggs ; Philippe Hascoat ; James R. Diers ; Jyoti Seth ; Robin K. Lammi ; David F. Bocian ; Dewey Holten ; and Jonathan S. Lindsey
• 刊名：Chemistry of Materials
• 出版年：2001
• 出版时间：March 2001
• 年：2001
• 卷：13
• 期：3
• 页码：1023 - 1034
• 全文大小：171K
• 年卷期：v.13,no.3(March 2001)
• ISSN：1520-5002

文摘

Two porphyrin-based optoelectronic gates and several prototypical redox-switchingcomponents of gates have been synthesized for studies in molecular photonics. Linear andT-shaped molecular optoelectronic gates contain a boron-dipyrrin (BDPY) dye as the inputunit, a zinc (Zn) porphyrin as the transmission unit, a free base (Fb) porphyrin as the outputunit, and a magnesium (Mg) porphyrin as the redox-switching unit. The linear gate and Tgate were synthesized using a molecular building block approach. In the linear gate synthesis,a BDPY-Zn porphyrin dyad was coupled with a Fb porphyrin-Mg porphyrin dimer. Thesynthesis of the T gate utilized a Zn porphyrin bearing four different meso substituents:mesityl, 4-iodophenyl, 4-[2-(trimethylsilyl)ethynyl]phenyl, and 4-[2-triisopropyl)ethynyl]phenyl. Attachment of the three different groups to the Zn porphyrin was accomplishedusing successive Pd-mediated coupling reactions in the following sequence: Fb porphyrin(output unit), BDPY dye (input unit), and Mg porphyrin (redox-switching unit). Both thelinear gate and T gate syntheses introduce the Mg porphyrin at the final step to minimizedemetalation of the Mg porphyrin. Refinements to various components of these gates wereinvestigated through the preparation of a ferrocene-porphyrin, a ferrocene-phthalocyanine,and a ferrocene-porphyrin-phthalocyanine. A dyad motif for studies of optically based redoxswitching was prepared that contains a derivative of Ru(bpy)₃X₂ coupled to a porphyrin.From these and related studies have emerged a number of design considerations for thedevelopment of refined optoelectronic gates.