Highly Crystalline and Semiconducting Imine‐Based Two‐Dimensional Polymers Enabled by Interfacial Synthesis

• Published in: Angewandte Chemie 2020-04, Vol.132 (15), p.6084-6092
• Main Authors: Sahabudeen, Hafeesudeen, Qi, Haoyuan, Ballabio, Marco, Položij, Miroslav, Olthof, Selina, Shivhare, Rishi, Jing, Yu, Park, SangWook, Liu, Kejun, Zhang, Tao, Ma, Ji, Rellinghaus, Bernd, Mannsfeld, Stefan, Heine, Thomas, Bonn, Mischa, Cánovas, Enrique, Zheng, Zhikun, Kaiser, Ute, Dong, Renhao, Feng, Xinliang
• Format: Article
• Language: English
• Subjects: 2D-Polymere; Chemical synthesis; Chemistry; Crystal structure; Crystallinity; Degree of crystallinity; Grenzflächensynthese; Halbleiter; Hole mobility; Imin-basierte COFs; Lattices; Multilayers; Optoelectronics; Photoleitfähigkeit; Polyimide resins; Polymer films; Polymers; Spectroscopy; Transport properties; Triazine
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201915217

Single‐layer and multi‐layer 2D polyimine films have been achieved through interfacial synthesis methods. However, it remains a great challenge to achieve the maximum degree of crystallinity in the 2D polyimines, which largely limits the long‐range transport properties. Here we employ a surfactant‐monolayer‐assisted interfacial synthesis (SMAIS) method for the successful preparation of porphyrin and triazine containing polyimine‐based 2D polymer (PI‐2DP) films with square and hexagonal lattices, respectively. The synthetic PI‐2DP films are featured with polycrystalline multilayers with tunable thickness from 6 to 200 nm and large crystalline domains (100–150 nm in size). Intrigued by high crystallinity and the presence of electroactive porphyrin moieties, the optoelectronic properties of PI‐2DP are investigated by time‐resolved terahertz spectroscopy. Typically, the porphyrin‐based PI‐2DP 1 film exhibits a p‐type semiconductor behavior with a band gap of 1.38 eV and hole mobility as high as 0.01 cm2 V−1 s−1, superior to the previously reported polyimine based materials. Drei kristalline Imin‐basierte 2D‐Polymerfilme wurden durch tensidmonolagenunterstützte Grenzflächensynthese (SMAIS) hergestellt. Die synthetischen PI‐2DP‐Filme sind mit polykristallinen Mehrfachlagen mit abstimmbarer Dicke von 6–200 nm und großen kristallinen Domänen (100–150 nm) ausgestattet und weisen p‐Halbleiterverhalten mit einer Bandlücke von 1.38 eV auf.