title: Fine-Tuning of Crystal Packing and Charge Transport Properties of BDOPV Derivatives through Fluorine Substitution.
abstract: Molecular packing in organic single crystals greatly influences their charge transport properties but can hardly be predicted and designed because of the complex intermolecular interactions. In this work, we have realized systematic fine-tuning of the single-crystal molecular packing of five benzodifurandione-based oligo(p-phenylenevinylene) (BDOPV)-based small molecules through incorporation of electronegative fluorine atoms on the BDOPV backbone. While these molecules all exhibit similar column stacking configurations in their single crystals, the intermolecular displacements and distances can be substantially modified by tuning of the amounts and/or the positions of the substituent fluorine atoms. Density functional theory calculations showed that the subtle differences in charge distribution or electrostatic potential induced by different fluorine substitutions play an important role in regulating the molecular packing of the BDOPV compounds. Consequently, the electronic couplings for electron transfer can vary from 71 meV in a slipped stack to 201 meV in a nearly cofacial antiparallel stack, leading to an increase in the electron mobility of the BDOPV derivatives from 2.6 to 12.6 cm(2) V(-1) s(-1). The electron mobility of the five molecules did not show a good correlation with the LUMO levels, indicating that the distinct difference in charge transport properties is a result of the molecular packing. Our work not only provides a series of high-electron-mobility organic semiconductors but also demonstrates that fluorination is an effective approach for fine-tuning of single-crystal packing modes beyond simply lowering the molecular energy levels.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Jin-Hu
authors.initials: JH
authors.lastname: Dou
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Yu-Qing
authors.initials: YQ
authors.lastname: Zheng
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Ze-Fan
authors.initials: ZF
authors.lastname: Yao
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Zhi-Ao
authors.initials: ZA
authors.lastname: Yu
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Ting
authors.initials: T
authors.lastname: Lei
authors.affiliation: Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
authors.forename: Xingxing
authors.initials: X
authors.lastname: Shen
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Xu-Yi
authors.initials: XY
authors.lastname: Luo
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Junliang
authors.initials: J
authors.lastname: Sun
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Shi-Ding
authors.initials: SD
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Yi-Fan
authors.initials: YF
authors.lastname: Ding
authors.affiliation: Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
authors.forename: Guangchao
authors.initials: G
authors.lastname: Han
authors.affiliation: Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
authors.forename: Yuanping
authors.initials: Y
authors.lastname: Yi
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Jie-Yu
authors.initials: JY
authors.lastname: Wang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Center of Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Jian
authors.initials: J
authors.lastname: Pei