Highly Efficient Preparation of Single-Layer Two-Dimensional Polymer Obtained from Single-Crystal to Single-Crystal...

A two-dimensional polymer (2DP) single crystal (T-2DP) with submillimeter size was synthesized by single-crystal to single-crystal transformation based on photochemical [2 + 2]-cycloaddition. A successful conversion from monomer to polymer was achieved in the single-crystal state. The structure information with an atomic resolution of both the monomer and 2DP was given through single-crystal X-ray diffraction. By simply treated with trifluoroacetic acid (TFA) under mild conditions, an unprecedented efficiency of exfoliation was achieved. The triazine core in T-2DP could be protonated by TFA, which resulted in a solution-like sample with >60% of monolayers. The size of the exfoliated monolayer reaches to several hundreds of μm². This is another precious example of 2DP single crystal with nearly perfect structure and large enough size. The successful preparation of the highly desirable 2DP "solution" for a long time containing large sized and large amount of 2DP monolayers may open up new prospects for the basic properties study and the applications of 2DPs.