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Mechanoactivated amorphization and photopolymerization of styryldipyryliums
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DOI：10.1038/s43246-024-00539-8.png)
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Abstract
En 中文
Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, which results in their amorphization-enabled solid-state photopolymerization and produces soluble and processable amorphous polymers. A combination of solid-state nuclear magnetic resonance, X-ray diffraction, and absorption/fluorescence spectroscopy reveals the crucial role of a mechanically-disordered monomer phase in yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, mechanoactivation and amorphization can expand the scope of topochemical polymerization conditions to open up opportunities for generating polymers that are otherwise difficult to synthesize and analyze. Mechanical grinding of crystals aids in converting photostable polymorph to a photoactive one but is not widely applied to organic polymers. Here, mechanoactivation and amorphization of photostable styryldipyrylium ionic monomers are demonstrated.
Keywords:
SOLID-STATE POLYMERIZATION
SINGLE-CRYSTAL
TOPOCHEMICAL POLYMERIZATION
SUPRAMOLECULAR CATALYSIS
2+2 PHOTODIMERIZATION
RECENT PROGRESS
ALKYNE GROUPS
CYCLOADDITION
ASSEMBLIES
POLYMERS
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