Modular Assembly of Poly(naphthalene diimide) and Ru(II) Dyes for an Efficient Light-Induced Charge Separation in Hierarchically Controlled Polymer Architectures

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• 作者：Robert Schroot ; Tina Schlotthauer ; Ulrich S. Schubert ; Michael Jäger
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：March 22, 2016
• 年：2016
• 卷：49
• 期：6
• 页码：2112-2123
• 全文大小：624K
• ISSN：1520-5835

文摘

Hierarchically well-defined multielectron acceptor–photosensitizer (A_n–P) assemblies were prepared by nitroxide-mediated polymerization of a styrenic naphthalene diimide and subsequent decoration of the chain terminus by a [Ru(dqp)₂]²⁺ photosensitizer (dqp is 2,6-di(quinolin-8-yl)pyridine). In view of a facile modular design, three synthetic linkage procedures were explored aiming at tailored light-initiated energy and electron transfer processes. The polymers were conveniently purified by column chromatography using amino- or diol-functionalized silica gels and were characterized in detail by NMR, MS, and UV−vis-SEC measurements. The electrochemical and absorption data confirmed the preserved individual redox and optical properties of the building blocks. The detailed steady-state emission measurements revealed an efficient quenching of the photosensitizer exceeding 86–96% with respect to reference complexes and the partial sensitization of/by polymer-based excited states. The results demonstrate the general versatility to construct photoredox-active macromolecules from tailored building blocks.