Diazulenorubicene as a Non-benzenoid Isomer of peri-Tetracene with Two Sets of 5/7/5 Membered Rings Showing Good Semiconducting Properties

Liyuan Qin; Yan-Ying Huang; Botao Wu; Jinliang Pan; Junfang Yang; Jing Zhang; Guangchao Han; Suyu Yang; Liangliang Chen; Zheng Yin; Yilin Shu; Lang Jiang; Yuanping Yi; Qian Peng; Xiong Zhou; Cheng Li; Guanxin Zhang; Xi-Sha Zhang; Kai Wu; Deqing Zhang

doi:10.1002/anie.202304632

Diazulenorubicene as a Non-benzenoid Isomer of peri-Tetracene with Two Sets of 5/7/5 Membered Rings Showing Good Semiconducting Properties

Angew Chem Int Ed Engl. 2023 Sep 25;62(39):e202304632. doi: 10.1002/anie.202304632. Epub 2023 Jul 3.

Authors

Liyuan Qin^{1

2}, Yan-Ying Huang^{1

2}, Botao Wu³, Jinliang Pan³, Junfang Yang², Jing Zhang¹, Guangchao Han¹, Suyu Yang¹, Liangliang Chen¹, Zheng Yin^{1

2}, Yilin Shu^{1

2}, Lang Jiang¹, Yuanping Yi¹, Qian Peng², Xiong Zhou³, Cheng Li¹, Guanxin Zhang¹, Xi-Sha Zhang^{1

2

4}, Kai Wu³, Deqing Zhang^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, CAS Center of Excellence in Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
² School of Chemical Sciences, University of Chinese Academy of Sciences, 100049, Beijing, China.
³ College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China.
⁴ State Key Laboratory of Applied Organic Chemistry, Lanzhou University, 730000, Lanzhou, China.

PMID: 37338996
DOI: 10.1002/anie.202304632

Abstract

Non-benzenoid polycyclic aromatic hydrocarbons (PAHs) have received a lot of attention because of their unique optical, electronic, and magnetic properties, but their synthesis remains challenging. Herein, we report a non-benzenoid isomer of peri-tetracene, diazulenorubicene (DAR), with two sets of 5/7/5 membered rings synthesized by a (3+2) annulation reaction. Compared with the precursor containing only 5/7 membered rings, the newly formed five membered rings switch the aromaticity of the original heptagon/pentagon from antiaromatic/aromatic to non-aromatic/antiaromatic respectively, modify the intermolecular packing modes, and lower the LUMO levels. Notably, compound 2 b (DAR-TMS) shows p-type semiconducting properties with a hole mobility up to 1.27 cm² V^-1 s^-1 . Moreover, further extension to larger non-benzenoid PAHs with 19 rings was achieved through on-surface chemistry from the DAR derivative with one alkynyl group.

Keywords: Annulation; Aromaticity; Fused Ring Systems; Semiconducting Properties; on-Surface Synthesis.

Abstract

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