On-Surface Debromination of C<sub>6</sub>Br<sub>6</sub>: C<sub>6</sub> Ring versus C<sub>6</sub> Chain.

Gao, Wenze; Kang, Faming; Qiu, Xia; Yi, Zewei; Shang, Lina; Liu, Mengxi; Qiu, Xiaohui; Luo, Yi et al. · ACS Nano · 2022

basic_science · Level V

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Abstract

Carbon allotropes comprising sp-hybridized carbon atoms have been investigated for decades for their molecular structure. One of the unsolved mysteries is whether they should take a linear or cyclic configuration in condensed phases due to the lack of atomistic characterizations. Herein, we designed a molecule with a C<sub>6</sub> skeleton as a model system to address this issue, which was achieved by eliminating Br atoms from hexabromobenzene (C<sub>6</sub>Br<sub>6</sub>) molecule on the Ag(111) substrate via thermal treatment. It is found that the C<sub>6</sub> ring intermediate resulting from complete debromination is energetically unstable at room temperature based on theoretical calculations. It subsequently transforms into the C<sub>6</sub> polyynic chain via a ring-opening process and ultimately polymerizes into the organometallic polyyne, whose triyne structural unit is revealed by bond-resolved noncontact atomic force microscopy. Theoretical calculations demonstrated an energetically favorable pathway in which the ring-opening process occurs after complete debromination of C<sub>6</sub>Br<sub>6</sub>. Our study provides a platform for the synthesis of elusive carbon-rich materials.