Crystallization induced enantiomer division (CIED) of π-expanded benzoacridine regioisomers. (November 2019)

• Record Type: Journal Article
• Authors: Zhao, Qiang; Li, Yihao; Wang, Zepeng; Wang, Jianfeng; Yan, Bohan; Yu, Yang; Li, Jiewei; Lin, Jinyi; Zhao, Jianfeng; Weng, Jiena; Zhao, Xianghua; Gao, Yongqian; Huang, Wei
• Is Part Of: Dyes and pigments. Volume 170(2019)
• Publication Date: 2019-11
• Subjects: Benzoacridine -- Crystallization -- Enantiomer division -- π-Expansion -- Intramolecular steric distortion; Dyes and dyeing -- Periodicals; Pigments -- Periodicals; 667.2
• DOI: 10.1016/j.dyepig.2019.107616
• Languages: English
• ISSNs: 0143-7208

Abstract

Abstract: Asymmetrical isomerization with prochiral π-distortion is useful to precisely construct nonplanar arenes as promising wide band gap (>2.2 eV) semiconductors. A series of asymmetrical benzoacridine regioisomers (ADs) were designed and obtained via a two-step procedure including Ullmann C-N coupling, intramolecular Friedel-Crafts ortho -aroylation. Interestingly, crystallization induced enantiomer division (CIED) of four prochiral ADs was observed. The corresponding ten divided enantiomers or diastereoisomers were carefully anatomized and distinguished from their "monozygotic and/or dizygotic twins" in crystals. The precise structures of four ADs were confirmed by 1 H NMR, 13 C NMR, HiRes MALDI-TOF MS, FT-IR and single crystal X-Ray diffraction. According to the absorbance spectra, ADs possess wide optical band gaps (2.90–2.98 eV) in film state and potential ability for high performed electronic devices. Graphical abstract: "The Big Bang of Acrid-Universe" : A family of four symmetrical benzoacridine analogues with π-expansion was discovered in the form of regioisomers, enantiomers, and diastereoisomers in single crystals. This interesting phenomenon is regarded as crystallization induced enantiomer division (CIED) behavior in favor of wide optical band gaps (2.90–2.98 eV) in film state as potential high performed materials for organic electronics.Image 1 Highlights: This work is the first systematical and accurate investigation on crystallization induced enantiomer division (CIED) phenomenon of prochiral and π-expanded benzoacridine regioisomers (ADs) with wide optical band gap. All four single crystals of four ADs provided the most direct and precise evidence to disclose the difficult, ambiguous, and misery "world" of asymmetrical isomerization including regioisomers, enantiomers, and diastereoisomers. This work clarified and figured out the relationship between the selectivity and competivity of Friedel-Crafts ortho- aroylation on the basis of 1-aminonaphthalene and 2-aminonaphthalene derived precursors of ADs.