Wafer-sized multifunctional polyimine-based two-dimensional conjugated polymers with high mechanical stiffness

Abstract

One of the key challenges in two-dimensional (2D) materials is to go beyond graphene, a prototype 2D polymer (2DP), and to synthesize its organic analogues with structural control at the atomic- or molecular-level. Here we show the successful preparation of porphyrin-containing monolayer and multilayer 2DPs through Schiff-base polycondensation reaction at an air–water and liquid–liquid interface, respectively. Both the monolayer and multilayer 2DPs have crystalline structures as indicated by selected area electron diffraction. The monolayer 2DP has a thickness of∼0.7 nm with a lateral size of 4-inch wafer, and it has a Young's modulus of 267±30 GPa. Notably, the monolayer 2DP functions as an active semiconducting layer in a thin film transistor, while the multilayer 2DP from cobalt-porphyrin monomer efficiently catalyses hydrogen generation from water. This work presents an advance in the synthesis of novel 2D materials for electronics and energy-related applications.

Makroskopische kristalline 2D‐Polymere

“…3 [142] unterhalb der Grçße typischer Monomere bewegt. [126,127] Eine zusätzliche Wechselwirkung bietet sich in Monomer 15 an, in dem ein Wassermolekülaus der Subphase als Ligand fürd as Co 2+ -Ion fungieren kann. Eine synthetisch wichtige Option, die sich an der Wasser/Luft-Grenzfläche erçffnet, besteht darin, in die wässrigen Subphase z.…”

“…Im letzten Beispiel befassen wir uns mit den Komonomeren 14 und 15, [127] die Aldehyde bzw.A mine tragen und komplementäre Partner in einer dynamischen Iminkondensation sind. [167,168] Basierend auf diesen Komonomeren wurde die Herstellung konjugierter Schichtstrukturen untersucht, sowohl an der Wasser/Luft-Grenzfläche als auch an der Grenzfläche zwischen zwei Flüssigkeiten.…”

Interfacial Synthesis of a Monolayered Fluorescent Two‐Dimensional Polymer through Dynamic Imine Chemistry

“…In this process, polymerization of monomers takes place directly at the interface of two phases and ends up with mono‐ or few‐ layered 2DPs. Several pioneering researches have been conducted by using different reactions such as Schiff base, [4+4] cycloaddition, and Glaser‐Hay coupling reaction . Among these reactions, dynamic imine chemistry at the air/water interface (Langmuir‐Blodgett method) has great potential for large‐scale production of highly crystalline 2D polymers due to its dynamic self‐healing process.…”

Imine‐Based Architectures at Surfaces and Interfaces: From Self‐Assembly to Dynamic Covalent Chemistry in 2D

“…[2][3][4][5][6] Both DCC and supramolecular chemistry are adaptable and modular because they allow for the selection and exchange of molecular components. [11] In particular,D CC includes the chemistry of disulfides, [12,13] acetals, [14,15] esters, [16,17] oxime, [18] boroxine, [19,20] alkynes, [21] and imines [22][23][24][25][26][27][28][29] to allow the generation of new covalents tructures. The equilibration processes are much faster in supramolecular systemsw hen compared to DCC systems, because in the latter the covalentb onds need to be broken and reformed.…”