Corannulene derivatives with low LUMO levels and dense convex–concave packing for n-channel organic field-effect transistors

Abstract

Electron-deficient corannulene derivatives incorporating cyano and imide groups into the corannulene core were synthesized, which showed low LUMO (lowest unoccupied molecular orbital) levels and dense convex-concave packing structures in single crystals. These two features help to realize the first n-channel organic field-effect transistors (OFETs) in air based on corannulene derivatives.

Corannulene‐Based Electron Acceptors: Combining Modular and Practical Synthesis with Electron Affinity and Solubility

“…Synthesis of 2:Aliterature procedure was adapted for the synthesis of 2. [30] 1 HNMR (400 MHz, CDCl 3 ) d 8.20 (br,2H), 7.64 (br,4H), 3.70 (m, 2H), 1.77-1.65 (m, 2H), 1.37 (s, 2H), 1.25 (s, 28 H), 0.87 (t, J = 6.8 Hz, 3H). 13 Synthesis of 3:T oad egassed solution of p-thiocresol (32 mg, 0.26 mmol) in DMI (3.5 mL) was added potassium t-butoxide (29 mg, 0.26 mmol) and stirred for 20 minutes under argon.…”

“…To test the feasibility of the aforementioned notion, initially, Sygula's corannulene dicarboxylate [37] was transformed into anhydride 1 and then an imide through reaction with octadecylamine( Scheme 1a). [30] The dibromo imide 2 was subjected to a substitution reactionw ith thiocresola nd trifluoromethylbenzene thiol to give 3 and 4.Atreatment with m-chloroperbenzoic acid (m-CPBA) oxidizes the sulfur atoms and provides sulfones 5 and 6.T he two sets of compounds would allow fora comparison to be made to evaluate the impact of the trifluoromethyl groupo nt he electronic properties. It also demonstratesm odularity of synthesis in which the identity of the commercial thiol can be altered.…”

“…[3][4][5][6][7][8][9][10][11][12][13][14] Corannulene imide, for instance,c an be easily accessed with bromidef unctionalities. [28][29][30] Such an imide group is valuable in the present context as an electron-withdrawing group, whichc ombines with the sulfones and the fluorinated fragments to lower the LUMO of the centrala romatic nucleus and simultaneously allows for the installation of al ong alkyl chain to enhances olubility of the molecule. Overall, therefore, we envisionedt hat such am odularm olecular design might provide ap ractical access to highly electron deficientm aterials with high solubilities.…”

Corannulene derivatives for organic electronics: From molecular engineering to applications

“…These derivatives have been applied in the fields of supramolecular chemistry [7][8][9][10], liquid crystals [11,12], chiroptical activity [7,13,14], bottom-up synthesis of carbon nanotubes [15], radicals [16][17][18][19][20] and lithium-ion cells [21]. Although its semiconducting properties are also interesting and have attracted considerable attention on the synthesis and basic characterization, the device performance based on corannulene derivatives has not been demonstrated until recently [22][23][24][25][26][27].…”

“…Fortunately, the rich chemistry of corannulene allows such on-demand rational design of different corannulene molecules. We and Pei et al have developed a series of corannulene derivatives and used them as p-channel [22], n-channel [23] and ambipolar materials [26]. In addition, we also used corannulene derivatives as non-fullerene acceptors in organic solar cells [24].…”