The Transfer Dehydrogenation Method Enables a Family of High Crystalline Benzimidazole-linked Cu (II)-phthalocyanine-based Covalent Organic Frameworks Films

Qingsong Zhang; Zhiheng Zhu; Liping Liu; Haojie Huang; Xianjie Chen; Yangshuang Bian; Mingchao Shao; Xiaofang Wei; Chengyu Wang; Dong Wang; Jichen Dong; Yunlong Guo; Yongfa Zhu; Yunqi Liu

doi:10.1002/anie.202319027

The Transfer Dehydrogenation Method Enables a Family of High Crystalline Benzimidazole-linked Cu (II)-phthalocyanine-based Covalent Organic Frameworks Films

Angew Chem Int Ed Engl. 2024 May 6;63(19):e202319027. doi: 10.1002/anie.202319027. Epub 2024 Apr 8.

Authors

Qingsong Zhang^{1

2}, Zhiheng Zhu^{1

2}, Liping Liu^{1

3}, Haojie Huang^{1

2}, Xianjie Chen⁴, Yangshuang Bian^{1

2}, Mingchao Shao^{1

2}, Xiaofang Wei^{1

2}, Chengyu Wang^{1

2}, Dong Wang^{1

2}, Jichen Dong^{1

2}, Yunlong Guo^{1

2}, Yongfa Zhu³, Yunqi Liu^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
² University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
³ Department of Chemistry, Tsinghua University, Beijing, Beijing, 100084, P. R. China.
⁴ State Key Laboratory of Environment-friendly Energy Materials, School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang, 621010, P. R. China.

PMID: 38488819
DOI: 10.1002/anie.202319027

Abstract

Heterocycle-linked phthalocyanine-based COFs with close-packed π-π conjugated structures are a kind of material with intrinsic electrical conductivity, and they are considered to be candidates for photoelectrical devices. Previous studies have revealed their applications for energy storage, gas sensors, and field-effect transistors. However, their potential application in photodetector is still not fully studied. The main difficulty is preparing high-quality films. In our study, we found that our newly designed benzimidazole-linked Cu (II)-phthalocyanine-based COFs (BICuPc-COFs) film can hardly formed with a regular aerobic oxidation method. Therefore, we developed a transfer dehydrogenation method with N-benzylideneaniline (BA) as a mild reagent. With this in hand, we successfully prepared a family of high crystalline BICuPc-COFs powders and films. Furthermore, both of these new BICuPc-COFs films showed high electrical conductivity (0.022-0.218 S/m), higher than most of the reported COFs materials. Due to the broad absorption and high conductivity of BICuPc-COFs, synaptic devices with small source-drain voltage (V_DS=1 V) were fabricated with response light from visible to near-infrared. Based on these findings, we expect this study will provide a new perspective for the application of conducting heterocycle-linked COFs in synaptic devices.

Keywords: benzimidazole-linked phthalocyanine Cu (II)-based COFs films; broad-spectrum synaptic devices; transfer dehydrogenation.