Titanocene as a New Acceptor (A) for Arylamine Donors (D) in D−π–A Chromophores

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• 作者：Jared A. Pienkos ; A. Danai Agakidou ; Carl O. Trindle ; D. Wolfgang Herwald ; Zikri Altun ; Paul S. Wagenknecht
• 刊名：Organometallics
• 出版年：2016
• 出版时间：August 22, 2016
• 年：2016
• 卷：35
• 期：16
• 页码：2575-2578
• 全文大小：316K
• 年卷期：0
• ISSN：1520-6041

文摘

Charge transfer (CT) transitions are relevant in the fields of solar energy conversion and nonlinear optical materials. Herein, a series of complexes with an alkynyl linkage between an aryl amine donor and a Ti^IV (titanocene) acceptor is reported. Each complex displays a strong (15000 < ε < 24,000 M^–1cm^–1), low-energy (520 < λ < 560 nm) absorption ascribed to an amine to Ti^IV ligand-to-metal CT. This characterization is supported by UV–vis spectroscopy, cyclic voltammetry, and TD-DFT calculations. These complexes are not photostable; therefore, an alternate architecture, wherein the amine donor is appended to the titanocene cyclopentadienyl ligand, has been designed. The molar absorptivity of the amine to Ti^IV CT in this latter architecture is lower (2100 M^–1 cm^–1), indicating weaker donor–acceptor coupling. This architecture is indeed much more photostable.