Impact of alkyl chain branching positions on molecular packing and electron transport of dimeric perylenediimide derivatives  

作　　者：Yuan Guo Guangchao Han Yuanping Yi 

机构地区：[1]Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences,Beijing 100190, China [2]University of Chinese Academy Sciences,Beijing 100049, China

出　　处：《Journal of Energy Chemistry》2019年第8期138-143,I0006,共7页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(Grant no.51773208,51803216);the Ministry of Science and Technology of China(Grant no.2014CB643506);the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDB12020200)

摘　　要：Side chains play a critical role in tuning intermolecular interaction and charge transport in organic semiconductors. Here, we have systematically investigated the impact of branching positions of the alkyl side chains on the molecular packing and electron transport properties of a series of bay-linked dimeric perylenediimide(PDI) derivatives by atomistic molecular dynamics simulations in combination with charge transfer rate theory and kinetic Monte Carlo simulations. The results show that despite of different branching positions of the alkyl chains,π–π stacking is effectively inhibited for all the dimeric PDI derivatives. As the branching position moves away from the PDI backbone, the appearance of the alkyl atoms around the PDI backbone will first decrease and then increase. Correspondingly, the short contacts between the PDI moieties are first enhanced and then reduced. In particular, when the branching position is at the third carbon atom, the intermolecular connectivity becomes the most effective and the electron mobility is significantly increased by 2 times.Side chains play a critical role in tuning intermolecular interaction and charge transport in organic semiconductors. Here, we have systematically investigated the impact of branching positions of the alkyl side chains on the molecular packing and electron transport properties of a series of bay-linked dimeric perylenediimide(PDI) derivatives by atomistic molecular dynamics simulations in combination with charge transfer rate theory and kinetic Monte Carlo simulations. The results show that despite of different branching positions of the alkyl chains, π –π stacking is effectively inhibited for all the dimeric PDI derivatives. As the branching position moves away from the PDI backbone, the appearance of the alkyl atoms around the PDI backbone will first decrease and then increase. Correspondingly, the short contacts between the PDI moieties are first enhanced and then reduced. In particular, when the branching position is at the third carbon atom, the intermolecular connectivity becomes the most effective and the electron mobility is significantly increased by 2 times.

关 键 词：Molecular PACKING Electron MOBILITY Branching position PERYLENEDIIMIDE 

分 类 号：O4[理学—物理]