“Spine Surgery” of Perylene Diimides with Covalent B–N Bonds toward Electron-Deficient BN-Embedded Polycyclic Aromatic Hydrocarbons

Abstract

BN-embedded polycyclic aromatic hydrocarbons (PAHs) with unique optoelectronic properties are underdeveloped relative to their carbonaceous counterparts due to the lack of suitable and facile synthetic methods. Moreover, the dearth of electron-deficient BN-embedded PAHs further hinders their application in organic electronics. Here we present the first facile synthesis of novel perylene diimide derivatives (B2N2-PDIs) featuring n-type B–N covalent bonds. The structures of these compounds are fully confirmed through the detailed characterizations with NMR, MS, and X-ray crystallography. Further investigation shows that the introduction of BN units significantly modifies the photophysical and electronic properties of these B2N2-PDIs and is further understood with the aid of theoretical calculations. Compared with the parent perylene diimides (PDIs), B2N2-PDIs exhibit deeper highest occupied molecular orbital energy levels, new absorption peaks in the high-energy region, hypsochromic shift of absorption and emission maxima, and decrement of photoluminescent quantum yields. Single-crystal field-effect transistors based on B2N2-PDIs showcase an electron mobility up to 0.35 cm2 V–1 s–1, demonstrating their potential application in optoelectronic materials.

A perylene five-membered ring diimide for organic semiconductors and π-expanded conjugated molecules

“…34 Notably, bromination of PDI39 with liquid bromine selectively occurred at the 6-, 12-positions of perylene, yielding PDI39-Br in 85% yield (Scheme 2). The chemical structure of PDI39-Br was characterized by 1 H NMR, 13 Next, we show that PDI39-Br can be transformed into expanded conjugated molecules with a five-membered ring diimide unit. Firstly, we successfully incorporated azulene units into the PDI39 skeleton to form new non-benzenoid conjugated molecules.…”

“…5–10 However, the core-variation of PDIs with five-membered ring imides has rarely been investigated. 11–13 In this communication, we report a perylene-2,3;8,9-tetracarboxylic acid diimide ( PDI39 , Scheme 1a) which contains two five-membered ring imides connected at the 2,3- and 8,9-positions of perylene.…”

Late-stage derivatization of a (B,O)2-doped perylene

“…1) that are readily available from borinic acid precursors via the Au( i )-catalyzed addition of aryl 2 BE–H bonds across ortho -positioned alkynyl substituents. 12,13 Structural isomers of B with fully embedded BN moieties, such as compound C , 14 and its corresponding bisimides D 15 were published by Wang and Pei et al (Fig. 1).…”

High-performance three-coordinated organoboron emitters for organic light-emitting diodes

“…In making efforts to develop facile synthesis methods, Pei's group as a representative has enriched optoelectronic PAHs with modified optoelectronic properties through the incorporation of B-N (boron-nitrogen) covalent bonds. 46 The B atom in these compounds is usually sp 2 -hybridized and is bonded to three substituents with s-bonds. The remaining p z orbital, which is empty and thus strongly electron-deficient, makes the threecoordinated B atom a strong electron-acceptor and electroncarrier.…”