{"title":"刚性柔性配体饰有镧系元素的硒钨酸盐和光致发光特性","authors":"","doi":"10.1016/j.cjsc.2024.100370","DOIUrl":null,"url":null,"abstract":"<div><p><span><span>Currently, organic-inorganic hybrid lanthanide-incorporated polyoxometalates (POMs) have emerged as a prominent research area. Herein, we employ a simple raw material assembly method to synthesize two neoteric mixed-organic-ligand-ornamented </span>lanthanide (Ln) incorporated selenotungstates [H</span><sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>16</sub>Na<sub>2</sub>[Ln<sub>4</sub>(H<sub>2</sub>O)<sub>6</sub>(HPZDA)<sub>2</sub>(HFMA)<sub>2</sub>W<sub>8</sub>O<sub>21</sub>][B-<em>α</em>-SeW<sub>9</sub>O<sub>33</sub>]<sub>4</sub>·29H<sub>2</sub>O (Ln = Sm<sup>3+</sup> (<strong>1</strong>), La<sup>3+</sup> (<strong>2</strong>); H<sub>2</sub>PZDA = 2,3-pyrazine dicarboxylic acid, H<sub>2</sub>FMA = fumaric acid). <strong>1</strong> and <strong>2</strong><span> are isomorphic with the polyanions constructed from four trivacant Keggin [B-</span><em>α</em>-SeW<sub>9</sub>O<sub>33</sub>]<sup>8–</sup> ({SeW<sub>9</sub>}) segments and a rigid-flexible-ligand-ornamented dodeca-nuclear W–Ln heterometallic [Ln<sub>4</sub>(H<sub>2</sub>O)<sub>6</sub>(HPZDA)<sub>2</sub>(HFMA)<sub>2</sub>W<sub>8</sub>O<sub>21</sub>]<sup>14+</sup><span> cluster. Moreover, the solid-state fluorescence spectrum of </span><strong>1</strong><span> at room temperature mainly exhibits the characteristic emission peak of Sm</span><sup>3+</sup> cations. Additionally, energy transfer from {SeW<sub>9</sub>} to Sm<sup>3+</sup> ions in <strong>1</strong> 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.</p></div>","PeriodicalId":10151,"journal":{"name":"Chinese Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":5.9000,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Rigid-flexible-ligand-ornamented lanthanide-incorporated selenotungstates and photoluminescence properties\",\"authors\":\"\",\"doi\":\"10.1016/j.cjsc.2024.100370\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span><span>Currently, organic-inorganic hybrid lanthanide-incorporated polyoxometalates (POMs) have emerged as a prominent research area. Herein, we employ a simple raw material assembly method to synthesize two neoteric mixed-organic-ligand-ornamented </span>lanthanide (Ln) incorporated selenotungstates [H</span><sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>16</sub>Na<sub>2</sub>[Ln<sub>4</sub>(H<sub>2</sub>O)<sub>6</sub>(HPZDA)<sub>2</sub>(HFMA)<sub>2</sub>W<sub>8</sub>O<sub>21</sub>][B-<em>α</em>-SeW<sub>9</sub>O<sub>33</sub>]<sub>4</sub>·29H<sub>2</sub>O (Ln = Sm<sup>3+</sup> (<strong>1</strong>), La<sup>3+</sup> (<strong>2</strong>); H<sub>2</sub>PZDA = 2,3-pyrazine dicarboxylic acid, H<sub>2</sub>FMA = fumaric acid). <strong>1</strong> and <strong>2</strong><span> are isomorphic with the polyanions constructed from four trivacant Keggin [B-</span><em>α</em>-SeW<sub>9</sub>O<sub>33</sub>]<sup>8–</sup> ({SeW<sub>9</sub>}) segments and a rigid-flexible-ligand-ornamented dodeca-nuclear W–Ln heterometallic [Ln<sub>4</sub>(H<sub>2</sub>O)<sub>6</sub>(HPZDA)<sub>2</sub>(HFMA)<sub>2</sub>W<sub>8</sub>O<sub>21</sub>]<sup>14+</sup><span> cluster. Moreover, the solid-state fluorescence spectrum of </span><strong>1</strong><span> at room temperature mainly exhibits the characteristic emission peak of Sm</span><sup>3+</sup> cations. Additionally, energy transfer from {SeW<sub>9</sub>} to Sm<sup>3+</sup> ions in <strong>1</strong> 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.</p></div>\",\"PeriodicalId\":10151,\"journal\":{\"name\":\"Chinese Journal of Structural Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.9000,\"publicationDate\":\"2024-06-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chinese Journal of Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0254586124002113\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0254586124002113","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
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。
Rigid-flexible-ligand-ornamented lanthanide-incorporated selenotungstates and photoluminescence properties
Currently, organic-inorganic hybrid lanthanide-incorporated polyoxometalates (POMs) have emerged as a prominent research area. Herein, we employ a simple raw material assembly method to synthesize two neoteric mixed-organic-ligand-ornamented lanthanide (Ln) incorporated selenotungstates [H2N(CH3)2]16Na2[Ln4(H2O)6(HPZDA)2(HFMA)2W8O21][B-α-SeW9O33]4·29H2O (Ln = Sm3+ (1), La3+ (2); H2PZDA = 2,3-pyrazine dicarboxylic acid, H2FMA = fumaric acid). 1 and 2 are isomorphic with the polyanions constructed from four trivacant Keggin [B-α-SeW9O33]8– ({SeW9}) segments and a rigid-flexible-ligand-ornamented dodeca-nuclear W–Ln heterometallic [Ln4(H2O)6(HPZDA)2(HFMA)2W8O21]14+ cluster. Moreover, the solid-state fluorescence spectrum of 1 at room temperature mainly exhibits the characteristic emission peak of Sm3+ cations. Additionally, energy transfer from {SeW9} to Sm3+ ions in 1 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.
期刊介绍：
Chinese Journal of Structural Chemistry “JIEGOU HUAXUE ”, an academic journal consisting of reviews, articles, communications and notes, provides a forum for the reporting and discussion of current novel research achievements in the fields of structural chemistry, crystallography, spectroscopy, quantum chemistry, pharmaceutical chemistry, biochemistry, material science, etc. Structural Chemistry has been indexed by SCI, CA, and some other prestigious publications.
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