Synthesis of Zigzag Carbon Nanobelts through Scholl Reactions

Abstract

Zigzag carbon nanobelts are a long-sought-after target for organic synthesis. Herein we report new strategies for designing and synthesizing unprecedented zigzag carbon nanobelts, which present a wave-like arrangement of hexagons in the unrolled lattice of (n,0) single wall carbon nanotubes (n=16 or 24). The precursors of these zigzag carbon nanobelts are hybrid cyclic arylene oligomers consisting of meta-phenylene and 2,6-naphthalenylene as well as para-phenylene units. The Scholl reactions of these cyclic arylene oligomers form multiple carbon-carbon bonds selectively at the α-positions of naphthalene units resulting in the corresponding zigzag carbon nanobelts. As monitored with fluorescence spectroscopy, one of these nanobelts binds C60 with an association constant as high as (6.6±1.1)×106 M-1 in the solution in toluene. Computational studies combining linear regression analysis and hypothetical homodesmotic reactions reveal that these zigzag nanobelts have strain in the range of 67.5 to 69.6 kcal mol-1 , and the ladderization step through Scholl reactions is accompanied by increase of strain as large as 69.6 kcal mol-1 . The successful synthesis of these nanobelts demonstrates the powerfulness and efficiency of Scholl reactions in synthesizing strained polycyclic aromatics.