Tunable Heck-Mizoroki Reaction of Dibromonaphthalene Diimide with Aryl Ethylenes: Design, Synthesis, and Characterization of Coplanar NDI-Based Conjugated Molecules

Chunling Gu; Yangxiong Li; Lu Xiao; Hongbing Fu; Dong Wang; Liang Cheng; Li Liu

doi:10.1021/acs.joc.7b02140

Tunable Heck-Mizoroki Reaction of Dibromonaphthalene Diimide with Aryl Ethylenes: Design, Synthesis, and Characterization of Coplanar NDI-Based Conjugated Molecules

J Org Chem. 2017 Dec 1;82(23):12806-12812. doi: 10.1021/acs.joc.7b02140. Epub 2017 Nov 2.

Authors

Chunling Gu^{1

2}, Yangxiong Li^{1

2}, Lu Xiao^{1

2}, Hongbing Fu^{1

3}, Dong Wang¹, Liang Cheng^{1

2}, Li Liu^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
² University of Chinese Academy of Sciences , Beijing 100049, China.
³ Beijing Key Laboratory for Optical Materials and Photonic Devices, Department of Chemistry, Capital Normal University , Beijing 100048, China.

PMID: 29068232
DOI: 10.1021/acs.joc.7b02140

Abstract

Rational design of coplanar NDI-based conjugated molecules was achieved by covalently connecting naphthalene diimide (NDI) units with aryl (Ar) groups through vinylene (V) linkers via Heck-Mizoroki reaction. Two series of products, diolefination products (ArVNDIVAr) and hydroxylated and mono-olefination products (HONDIVAr), can be obtained, respectively, in moderate to excellent yields (45-90%) under controlled conditions, in which catalyst and base play the key roles. Density functional theory calculation discloses the outstanding planarity of the two types of products. Large bathochromic shifts are observed in both the absorbance and photoluminescence spectra of the HONDIVAr (144 and 229 nm) and ArVNDIVAr (180 and 242 nm) π-systems. Bathochromic shifts can be adjusted within the broad wavelength range by introducing 4'-substituents, either electron-withdrawing group (NO₂) or electron-donating group (NMe₂), in the phenyl group of aryl ethylenes. ArVNDIVArs show bigger bathochromic shifts than HONDIVArs.

Publication types

Research Support, Non-U.S. Gov't