Insight into stable,concentrated radicals from sulfur-functionalized alkyne-rich crystalline frameworks and application in solar-to-vapor conversion

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外文摘要：Organic radicals feature versatile unpaired electrons key for photoelectronic and biomedical applications but remain difficult to access in stable concentrated forms.We disclose easy generation of stable,concentrated radicals from various alkynyl phenyl motifs,including 1)sulfur-functionalized alkyne-rich organic linkers in crystalline frameworks;2)the powders of these molecules alone;3)simple diethynylbenzenes.For Zr-based framework,the generation of radical-rich crystalline framework was achieved by thermal annealing in the range of 300-450 ℃.For terminal alkynes,electron paramagnetic resonance signals(EPR,indicative of free radicals)arise after air exposure or mild heating(e.g,70 ℃).Further heating(e.g.,150 ℃ for 3 h)raises the radical concentrations up to 3.30 mol kg-1.For more stable internal alkynes,transformations into porous radical solids can also be triggered,albeit at higher temperatures(e.g.,250-500 ℃).The resulted radical-containing solids are porous,stable to air as well as heat(up to 300-450 ℃)and exhibit photothermal conversion and solar-driven water evaporation capacity.The formation of radicals can be ascribed to extensive alkyne cycliza-tions,forming defects,dangling bonds and the associated radicals stabilized by polycyclic π-systems.

外文关键词：

Porous coordination polymersPersistent radicalsNanographenePhotothermal conversionSolar-to-vapor conversion

作者：

Jian-Rong Li、Jieying Hu、Lai-Hon Chung、Jilong Zhou、Parijat Borah、Zhiqing Lin、Yuan-Hui Zhong、Hua-Qun Zhou、Xianghua Yang、Zhengtao Xu、Jun He

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作者单位：

School of Chemical Engineering and Light Industry,Guangdong University of Technology,Guangzhou,510006,China

Guangdong Provincial Laboratory of Chemistry and Fine Chemical Engineering Jieyang Center,Jieyang,515200,China

Institute of Materials Research and Engineering(IMRE),Agency for Science,Technology and Research(A*STAR),2 Fusionopolis Way,Singapore,138634,Republic of Singapore

基金：

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaFoundation of Basic and Applied Basic Research of Guangdong ProvinceFoundation of Basic and Applied Basic Research of Guangdong ProvinceScience and Technology Planning Project of Guangdong ProvinceScience and Technology Planning Project of Guangdong Provincestartup fund from A*STAR

项目编号：

22371054223010452020B15151200242024A15150128012021A05050300662023A0505050164SC25/22-119116

出版年：

2024

DOI：

10.1016/j.cjsc.2024.100380

结构化学

中国化学会中国科学院福建物质结构研究所

结构化学

影响因子：0.44

ISSN：0254-5861

年,卷(期)：2024.43(8)