Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058, Erlangen, Germany.
Departamento de Química Orgánica, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain.
Angew Chem Int Ed Engl. 2016 Apr 25;55(18):5560-4. doi: 10.1002/anie.201601258. Epub 2016 Mar 24.
A cycloaddition-retroelectrocyclization reaction between tetracyanoethylene and two zinc phthalocyanines (Zn(II) Pcs) bearing one or four anilino-substituted alkynes has been used to install a strong, electron-accepting tetracyanobuta-1,3-diene (TCBD) between the electron-rich Zn(II) Pc and aniline moieties. A combination of photophysical, electrochemical, and spectroelectrochemical investigations with the Zn(II) Pc-TCBD-aniline conjugates, which present panchromatic absorptions in the visible region extending all the way to the near infrared, show that the formal replacement of the triple bond by TCBD has a dramatic effect on their ground- and excited-state features. In particular, the formation of extremely intense, ground-state charge-transfer interactions between Zn(II) Pc and the electron-accepting TCBD were observed, something unprecedented not only in Pc chemistry but also in TCBD-based porphyrinoid systems.
四氰乙烯（TCNE）与两个锌酞菁（Zn(II) Pc）之间的环加成-反电环化反应被用来在富电子的 Zn(II) Pc 和苯胺部分之间安装一个强的电子受体四氰基丁二烯（TCBD）。Zn(II) Pc-TCBD-苯胺缀合物的光物理、电化学和光谱电化学研究的结合，在可见区域呈现全色吸收，一直延伸到近红外，表明三重键被 TCBD 取代的形式对其基态和激发态特征有显著影响。特别是，观察到 Zn(II) Pc 和强电子受体 TCBD 之间形成了极其强烈的基态电荷转移相互作用，这不仅在酞菁化学中，而且在基于 TCBD 的卟啉类系统中也是前所未有的。
