Elaborately Tuning Intramolecular Electron Transfer Through Varying Oligoacene Linkers in the Bis(diarylamino) Systems.
The research efforts on oligoacene systems are still relatively limited mainly due to the synthetic challenge and the extreme instability of longer acenes. Herein, these two issues have been overcome through elaborative modification and the stable pentacene species has been successfully synthesized. Additionally, a series of bis(diarylamino) compounds linked by variable-length oligoacene bridges ranging from one to five fused rings (benzene (1a), naphthalene (1b), anthracene (1c), tetracene (1d) and pentacene (1e)) have been prepared to probe the effect of the extent of π-conjugation on the electron transfer properties. Compound 1c exhibits a high planarity between the anthracyl bridge and the two nitrogen cores and the molecular packing shows a two-dimensional herringbone characteristic. Combined studies based on electrochemistry and spectroelectrochemistry demonstrate that (i) the electronic coupling across the oligoacene linkers between two diarylamine termini exponentially decrease with a moderate attenuation constant (β) of 0.14 Å-1in these length-modulated systems and (ii) the associated radical cations [1a]+-[1e]+are classified as the class II Robin-Day mixed-valence systems. Furthermore, density functional theory (DFT) calculations have been conducted to gain insight into the nature of electron transfer processes in these oligoacene systems.
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Jing
J
Zhang
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang, Jiangxi 330013, P. R. China.
Zhao
Z
Chen
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Lan
L
Yang
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Fang-Fang
FF
Pan
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Guang-Ao
GA
Yu
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Jun
J
Yin
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Sheng Hua
SH
Liu