Junichi Usuba, Zhenhuan Sun, Han P. Q. Nguyen, Cijil Raju, Klaus Schmidt-Rohr, Grace G. D. Han
{"title":"Mechanoactivated amorphization and photopolymerization of styryldipyryliums","authors":"Junichi Usuba, Zhenhuan Sun, Han P. Q. Nguyen, Cijil Raju, Klaus Schmidt-Rohr, Grace G. D. Han","doi":"10.1038/s43246-024-00539-8","DOIUrl":null,"url":null,"abstract":"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.","PeriodicalId":10589,"journal":{"name":"Communications Materials","volume":null,"pages":null},"PeriodicalIF":7.5000,"publicationDate":"2024-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s43246-024-00539-8.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Communications Materials","FirstCategoryId":"1085","ListUrlMain":"https://www.nature.com/articles/s43246-024-00539-8","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
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.
期刊介绍:
Communications Materials, a selective open access journal within Nature Portfolio, is dedicated to publishing top-tier research, reviews, and commentary across all facets of materials science. The journal showcases significant advancements in specialized research areas, encompassing both fundamental and applied studies. Serving as an open access option for materials sciences, Communications Materials applies less stringent criteria for impact and significance compared to Nature-branded journals, including Nature Communications.