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, generation of radical-rich crystalline framework was achieved by thermal annealing in the range of 300–450 °C. For terminal alkynes, electron paramagnetic resonance signals (EPR; indicative of free radicals) arise after air exposure or mild heating (, 70 °C). Further heating (, 150 °C for 3 h) raises the radical concentrations up to 3.30 mol kg. For the more stable internal alkynes, transformations into porous radical solids can also be triggered, albeit at higher temperatures (, 250–500 °C). The resulted radical-containing solids are porous, stable to air as well as heat (up to 300–450 °C) and exhibit photothermal conversion and solar-driven water evaporation capacity. The formation of radicals can be ascribed to extensive alkyne cyclizations, forming defects, dangling bonds and the associated radicals stabilized by the polycyclic π-systems.
有机自由基具有多功能的非配对电子，是光电子和生物医学应用的关键，但仍然难以获得稳定的浓缩形式。我们揭示了从各种炔基苯基基团（包括 1）结晶框架中的硫功能化富含炔基的有机连接体；2）这些分子的单独粉末；3）简单的二乙炔苯）中生成稳定、浓缩自由基的简单方法。对于锆基框架，可通过 300-450 °C 的热退火生成富含自由基的晶体框架。对于末端炔烃，在空气中暴露或轻度加热（70 °C）后会产生电子顺磁共振信号（EPR；表明自由基）。进一步加热（150 °C 3 小时）可使自由基浓度升高至 3.30 摩尔千克。对于更稳定的内部炔烃，尽管温度更高（250-500 °C），但也能引发向多孔自由基固体的转化。生成的含自由基固体多孔，对空气和热量（高达 300-450 ℃）稳定，并具有光热转换和太阳能驱动的水蒸发能力。自由基的形成可归因于广泛的炔烃环化作用，形成缺陷、悬挂键和由多环 π 系统稳定的相关自由基。
{"title":"Insight into stable, concentrated radicals from sulfur-functionalized alkyne-rich crystalline frameworks and application in solar-to-vapor conversion","authors":"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","doi":"10.1016/j.cjsc.2024.100380","DOIUrl":"https://doi.org/10.1016/j.cjsc.2024.100380","url":null,"abstract":"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, generation of radical-rich crystalline framework was achieved by thermal annealing in the range of 300–450 °C. For terminal alkynes, electron paramagnetic resonance signals (EPR; indicative of free radicals) arise after air exposure or mild heating (, 70 °C). Further heating (, 150 °C for 3 h) raises the radical concentrations up to 3.30 mol kg. For the more stable internal alkynes, transformations into porous radical solids can also be triggered, albeit at higher temperatures (, 250–500 °C). The resulted radical-containing solids are porous, stable to air as well as heat (up to 300–450 °C) and exhibit photothermal conversion and solar-driven water evaporation capacity. The formation of radicals can be ascribed to extensive alkyne cyclizations, forming defects, dangling bonds and the associated radicals stabilized by the polycyclic π-systems.","PeriodicalId":10151,"journal":{"name":"Chinese Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141512243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1016/j.cjsc.2024.100381
Jia-hui Li, Jinkai Qiu, Cheng Lian
{"title":"Lithium-ion rapid transport mechanism and channel design in solid electrolytes","authors":"Jia-hui Li, Jinkai Qiu, Cheng Lian","doi":"10.1016/j.cjsc.2024.100381","DOIUrl":"https://doi.org/10.1016/j.cjsc.2024.100381","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"Chinese Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141512244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Currently, organic–inorganic hybrid lanthanide-incorporated polyoxometalates (POMs) have emerged as a prominent research area. Herein, we employed a simple raw material assembly method to synthesize two neoteric mixed-organic -ligand-ornamented lanthanide (Ln) incorporated selenotungstates [HN(CH)]Na [Ln(HO)(HPZDA)(HFMA)WO][B--SeWO]·29HO (Ln = Sm (), La (); HPZDA = 2,3-pyrazine dicarboxylic acid, HFMA = fumaric acid). and are isomorphic with the polyanions constructed from four trivacant Keggin [B--SeWO] ({SeW}) segments and a rigid-flexible-ligand-ornamented dodeca-nuclear W–Ln heterometallic [Ln(HO)(HPZDA)(HFMA)WO] cluster. Moreover, the solid-state fluorescence spectrum of at room temperature mainly exhibits the characteristic emission peak of Sm cations. Additionally, energy transfer from {SeW} to Sm ions in has been demonstrated by time-resolved spectroscopy. This work presents a feasible dual-ligand synergistic strategy for constructing novel POM derivatives and POM-based fluorescent materials.
目前，有机-无机混合镧系元素掺杂聚氧化金属盐（POMs）已成为一个突出的研究领域。在此，我们采用简单的原料组装方法合成了两种新有机混合配体镧系元素（Ln）掺杂硒钨酸盐[HN(CH)]Na [Ln(HO)(HPZDA)(HFMA)WO][B--SeWO]-29HO （Ln = Sm（），La（）；HPZDA = 2,3-吡嗪二羧酸，HFMA = 富马酸）。并与由四个三价凯金[B--SeWO]（{SeW}）段和刚-柔-配体-饰十二核 W-Ln 异金属[Ln(HO)(HPZDA)(HFMA)WO]簇构建的多阴离子同构。此外，室温下的固态荧光光谱主要呈现出 Sm 阳离子的特征发射峰。此外，时间分辨光谱也证明了{SeW}向 Sm 离子的能量转移。这项工作为构建新型 POM 衍生物和基于 POM 的荧光材料提供了一种可行的双配体协同策略。
{"title":"Rigid-flexible-ligand-ornamented lanthanide-incorporated selenotungstates and photoluminescence properties","authors":"Tiantian Gong, Yanan Chen, Shuo Wang, Miao Wang, Junwei Zhao","doi":"10.1016/j.cjsc.2024.100370","DOIUrl":"https://doi.org/10.1016/j.cjsc.2024.100370","url":null,"abstract":"Currently, organic–inorganic hybrid lanthanide-incorporated polyoxometalates (POMs) have emerged as a prominent research area. Herein, we employed a simple raw material assembly method to synthesize two neoteric mixed-organic -ligand-ornamented lanthanide (Ln) incorporated selenotungstates [HN(CH)]Na [Ln(HO)(HPZDA)(HFMA)WO][B--SeWO]·29HO (Ln = Sm (), La (); HPZDA = 2,3-pyrazine dicarboxylic acid, HFMA = fumaric acid). and are isomorphic with the polyanions constructed from four trivacant Keggin [B--SeWO] ({SeW}) segments and a rigid-flexible-ligand-ornamented dodeca-nuclear W–Ln heterometallic [Ln(HO)(HPZDA)(HFMA)WO] cluster. Moreover, the solid-state fluorescence spectrum of at room temperature mainly exhibits the characteristic emission peak of Sm cations. Additionally, energy transfer from {SeW} to Sm ions in has been demonstrated by time-resolved spectroscopy. This work presents a feasible dual-ligand synergistic strategy for constructing novel POM derivatives and POM-based fluorescent materials.","PeriodicalId":10151,"journal":{"name":"Chinese Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141512247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-20DOI: 10.1016/j.cjsc.2024.100376
Kun Tang, Yu-Wu Zhong
{"title":"Water reduction by an organic single-chromophore photocatalyst","authors":"Kun Tang, Yu-Wu Zhong","doi":"10.1016/j.cjsc.2024.100376","DOIUrl":"https://doi.org/10.1016/j.cjsc.2024.100376","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"Chinese Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141512248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-01DOI: 10.1016/j.cjsc.2024.100256
Xin Dong , Tianqi Chen , Jing Liang , Lei Wang , Huajie Wu , Zhijin Xu , Junhua Luo , Li-Na Li
Metal halide perovskites have made significant progress in X-ray detection owing to their exceptional optoelectronic properties. However, most of these materials suffer from toxic element lead and require for high operating voltages. Hence, it is imperative to explore environmentally friendly perovskite crystals without external bias for X-ray detection. Herein, we strategically introduce chiral cations to synthesize a pair of lead-free chiral-polar hybrid perovskites (S-MPz)6Bi3I21·6H2O and (R-MPz)6Bi3I21·6H2O (1S and 1R, S/R-MPz = S/R-2-methylpiperazinium), which exhibit strong circular dichroism (CD) signals with an anisotropic g-factor reaching approximately 0.017. Significantly, the chiral-polar feature gives rise to distinctive spontaneous polarization, which leads to a photovoltage of 1.1 V under X-ray illumination, endowing self-powered detection capabilities for X-ray. Further exploration of X-ray devices based on 1R single crystal (SC) demonstrates a high sensitivity of 5.2 μC Gyair−1 cm−2 at zero bias. This study realizes passive X-ray detection depending on the intrinsic spontaneous polarization induced built-in electric field of chiral-polar perovskite, providing an effective approach to the chemical design of desired materials for high-performance “green” self-powered radiation detection.
金属卤化物过氧化物晶体因其卓越的光电特性，在 X 射线探测领域取得了重大进展。然而，这些材料大多含有有毒元素铅，并且需要很高的工作电压。因此，当务之急是探索用于 X 射线探测的无外部偏压的环境友好型过氧化物晶体。在这里，我们战略性地引入了手性阳离子，合成了一对无铅手性-极性混合包晶石 (-MPz)BiI-6HO 和 (-MPz)BiI-6HO （和 /MPz = /-2-甲基哌嗪），它们表现出强烈的圆二色性信号，各向异性-因子达到约 0.017。值得注意的是，手性极性特征产生了独特的自发极化，在 X 射线照射下可产生 1.1 V 的光电压，从而赋予了 X 射线自供电探测能力。对基于单晶体的 X 射线装置的进一步探索表明，在零偏压下，该装置具有 5.2 μC Gy cm 的高灵敏度。这项研究利用手性极性包晶的内在自发极化诱导内置电场实现了无源 X 射线探测，为高性能 "绿色 "自供电辐射探测所需材料的化学设计提供了有效方法。
{"title":"Structure design of lead-free chiral-polar perovskites for sensitive self-powered X-ray detection","authors":"Xin Dong , Tianqi Chen , Jing Liang , Lei Wang , Huajie Wu , Zhijin Xu , Junhua Luo , Li-Na Li","doi":"10.1016/j.cjsc.2024.100256","DOIUrl":"10.1016/j.cjsc.2024.100256","url":null,"abstract":"<div><p>Metal halide perovskites have made significant progress in X-ray detection owing to their exceptional optoelectronic properties. However, most of these materials suffer from toxic element lead and require for high operating voltages. Hence, it is imperative to explore environmentally friendly perovskite crystals without external bias for X-ray detection. Herein, we strategically introduce chiral cations to synthesize a pair of lead-free chiral-polar hybrid perovskites (<em>S</em>-MPz)<sub>6</sub>Bi<sub>3</sub>I<sub>21</sub>·6H<sub>2</sub>O and (<em>R</em>-MPz)<sub>6</sub>Bi<sub>3</sub>I<sub>21</sub>·6H<sub>2</sub>O (<strong>1<em>S</em></strong> and <strong>1<em>R</em></strong>, <em>S</em>/<em>R-</em>MPz = <em>S</em>/<em>R</em>-2-methylpiperazinium), which exhibit strong circular dichroism (CD) signals with an anisotropic <em>g</em>-factor reaching approximately 0.017. Significantly, the chiral-polar feature gives rise to distinctive spontaneous polarization, which leads to a photovoltage of 1.1 V under X-ray illumination, endowing self-powered detection capabilities for X-ray. Further exploration of X-ray devices based on <strong>1<em>R</em></strong> single crystal (SC) demonstrates a high sensitivity of 5.2 μC Gy<sub>air</sub><sup>−1</sup> cm<sup>−2</sup> at zero bias. This study realizes passive X-ray detection depending on the intrinsic spontaneous polarization induced built-in electric field of chiral-polar perovskite, providing an effective approach to the chemical design of desired materials for high-performance “green” self-powered radiation detection.</p></div>","PeriodicalId":10151,"journal":{"name":"Chinese Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140056482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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