Open AccessElaborately Tuning Intramolecular Electron Transfer Through Varying Oligoacene Linkers in the Bis(diarylamino) Systems
Author(s) -
Jing Zhang,
Chen-Liang Zhao,
Liying Yang,
Fangfang Pan,
GuangAo Yu,
Jun Yin,
Sheng Hua Liu
Publication year - 2016
Publication title -
scientific reports
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.24
H-Index - 213
ISSN - 2045-2322
DOI - 10.1038/srep36310
Subject(s) - pentacene , tetracene , intramolecular force , anthracene , electron transfer , density functional theory , planarity testing , chemistry , valence (chemistry) , chemical physics , materials science , photochemistry , computational chemistry , crystallography , stereochemistry , organic chemistry , thin film transistor , electrode
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 −1 in 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.