Rational Functionalization of a C70 Buckybowl To Enable a C70:Buckybowl Cocrystal for Organic Semiconductor Applications

• Published in: Journal of the American Chemical Society Vol. 142; no. 5; pp. 2460 - 2470
• Main Authors: Gao, Guangpeng, Chen, Meng, Roberts, Josiah, Feng, Meng, Xiao, Chengyi, Zhang, Guowei, Parkin, Sean, Risko, Chad, Zhang, Lei
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 05.02.2020; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; CORANNULENE; GEODESIC POLYARENES; BOWL-SHAPED FRAGMENTS; STRUCTURAL-ANALYSIS; CHARGE-TRANSPORT; FULLERENES SYNTHESIS; CRYSTAL; C-60; FIELD-EFFECT TRANSISTORS; ELECTRON-ACCEPTORS
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.9b12192

Fullerene fragments, referred to as buckybowls, are garnering interest due to their distinctive molecular shapes and optoelectronic properties. Here, we report the synthesis and characterization of a novel C70 subunit, diindeno­[4,3,2,1-fghi:4′,3′,2′,1′-opqr]­perylene, that is substituted with either triethylsilyl­(TES)-ethynyl or 2,4,6-triisopropylphenyl groups at the meta-positions. The resulting compounds (1 and 2) display a bowl-to-bowl inversion at room temperature. Notably, the substituent groups on the meta-positions alter both the geometric and the electronic properties as well as the crystal packing of the buckybowls. In contrast to the 2,4,6-triisopropylphenyl groups in 2, the TES-ethynyl groups in 1 lead to enhanced bond length alternation, resulting in weaker aromaticity of the six-membered rings of the buckybowl skeleton. 1 forms one-dimensional (1D) concave-in-convex stacking columns, and when 1 is blended with C70, the buckybowls encapsulate C70 and result in two-dimensional cocrystals. Organic field-effect transistor (OFET) measurements demonstrate that 1 displays a hole mobility of 0.31 cm2 V–1 s–1, and the 1-C70 cocrystal exhibits ambipolar transport characteristics with electron and hole mobilities approaching 0.40 and 0.07 cm2 V–1 s–1, respectively. This work demonstrates the potential of buckybowls for the development of organic semiconductors.