Linmeng Xu, Tianxia Chen, Kun Zhou, Baokuan Chen, Yanfeng Bi
{"title":"可调谐发光的磺酰基钙[4]炔支撑 Ln8(Ln = Tb 和 Eu)配位轮中的离子位点置换","authors":"Linmeng Xu, Tianxia Chen, Kun Zhou, Baokuan Chen, Yanfeng Bi","doi":"10.1021/acs.cgd.4c00682","DOIUrl":null,"url":null,"abstract":"Lanthanide coordination clusters (LCCs), namely, [Ln<sub>8</sub>(TC4A-SO<sub>2</sub>)<sub>4</sub>(TA)<sub>2</sub>(DMF)<sub>4</sub>(H<sub>2</sub>O)<sub>10</sub>] (solvents) (Ln<sub>8</sub> = <b>Tb</b><sub><b>8</b></sub>, <b>Eu</b><sub><b>8</b></sub>, <b>Tb</b><sub><b>4</b></sub><b>Eu</b><sub><b>4</b></sub>; H<sub>4</sub>TC4A-SO<sub>2</sub> = <i>p</i>-<i>tert</i>-butylsulfonylcalix[4]arene; H<sub>4</sub>TA = <span>dl</span>-tartaric acid), were synthesized via the solvothermal method and were characterized by single-crystal X-ray diffraction. Ln<sub>8</sub> is a wheel-shaped framework built from four cone-shaped mononuclear units (Ln<sup>III</sup>-TC4A-SO<sub>2</sub>) and four bridging-Ln<sup>III</sup> ions with two tartrates located in the center serving as “spokes”. <b>Tb</b><sub><b>8</b></sub> exhibits an extraordinary luminescence quantum yield (QY<sub>s</sub>) of 53.3% in the solid state under the excitation of 370 nm, while <b>Eu</b><sub><b>8</b></sub> cannot emit under similar conditions. Furthermore, <b>Tb</b><sub><b>8</b></sub> shows concentration-dependent emission in a methanol solution with the best luminescence QY<sub>l</sub> of 61.8%, representing one of the best luminescent Tb-based coordination clusters. The Eu ions can be rationally doped in the Tb ring (<b>Tb</b><sub><i>x</i></sub><b>Eu</b><sub><b>8–<i>x</i></b></sub>, 4 ≤ <i>x</i> < 8) by a stoichiometric ratio on specific sites to tune the emission color output, which reveals the efficient energy transfer from <sup>5</sup>D<sub>4</sub>-<sup>7</sup>F<sub>5</sub> and <sup>5</sup>D<sub>4</sub>-<sup>7</sup>F<sub>6</sub> levels of Tb<sup>III</sup> to the <sup>5</sup>D<sub>0</sub> level of Eu<sup>III</sup>. This work presents a unique method of controlling the fabrication and tunable luminescence of LCCs.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"3 1","pages":""},"PeriodicalIF":3.2000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ion Site Substitution in a Sulfonylcalix[4]arene-Supported Ln8 (Ln = Tb and Eu) Coordination Wheel with Tunable Luminescence\",\"authors\":\"Linmeng Xu, Tianxia Chen, Kun Zhou, Baokuan Chen, Yanfeng Bi\",\"doi\":\"10.1021/acs.cgd.4c00682\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Lanthanide coordination clusters (LCCs), namely, [Ln<sub>8</sub>(TC4A-SO<sub>2</sub>)<sub>4</sub>(TA)<sub>2</sub>(DMF)<sub>4</sub>(H<sub>2</sub>O)<sub>10</sub>] (solvents) (Ln<sub>8</sub> = <b>Tb</b><sub><b>8</b></sub>, <b>Eu</b><sub><b>8</b></sub>, <b>Tb</b><sub><b>4</b></sub><b>Eu</b><sub><b>4</b></sub>; H<sub>4</sub>TC4A-SO<sub>2</sub> = <i>p</i>-<i>tert</i>-butylsulfonylcalix[4]arene; H<sub>4</sub>TA = <span>dl</span>-tartaric acid), were synthesized via the solvothermal method and were characterized by single-crystal X-ray diffraction. Ln<sub>8</sub> is a wheel-shaped framework built from four cone-shaped mononuclear units (Ln<sup>III</sup>-TC4A-SO<sub>2</sub>) and four bridging-Ln<sup>III</sup> ions with two tartrates located in the center serving as “spokes”. <b>Tb</b><sub><b>8</b></sub> exhibits an extraordinary luminescence quantum yield (QY<sub>s</sub>) of 53.3% in the solid state under the excitation of 370 nm, while <b>Eu</b><sub><b>8</b></sub> cannot emit under similar conditions. Furthermore, <b>Tb</b><sub><b>8</b></sub> shows concentration-dependent emission in a methanol solution with the best luminescence QY<sub>l</sub> of 61.8%, representing one of the best luminescent Tb-based coordination clusters. The Eu ions can be rationally doped in the Tb ring (<b>Tb</b><sub><i>x</i></sub><b>Eu</b><sub><b>8–<i>x</i></b></sub>, 4 ≤ <i>x</i> < 8) by a stoichiometric ratio on specific sites to tune the emission color output, which reveals the efficient energy transfer from <sup>5</sup>D<sub>4</sub>-<sup>7</sup>F<sub>5</sub> and <sup>5</sup>D<sub>4</sub>-<sup>7</sup>F<sub>6</sub> levels of Tb<sup>III</sup> to the <sup>5</sup>D<sub>0</sub> level of Eu<sup>III</sup>. This work presents a unique method of controlling the fabrication and tunable luminescence of LCCs.\",\"PeriodicalId\":34,\"journal\":{\"name\":\"Crystal Growth & Design\",\"volume\":\"3 1\",\"pages\":\"\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-09-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Crystal Growth & Design\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.cgd.4c00682\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.cgd.4c00682","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Ion Site Substitution in a Sulfonylcalix[4]arene-Supported Ln8 (Ln = Tb and Eu) Coordination Wheel with Tunable Luminescence
Lanthanide coordination clusters (LCCs), namely, [Ln8(TC4A-SO2)4(TA)2(DMF)4(H2O)10] (solvents) (Ln8 = Tb8, Eu8, Tb4Eu4; H4TC4A-SO2 = p-tert-butylsulfonylcalix[4]arene; H4TA = dl-tartaric acid), were synthesized via the solvothermal method and were characterized by single-crystal X-ray diffraction. Ln8 is a wheel-shaped framework built from four cone-shaped mononuclear units (LnIII-TC4A-SO2) and four bridging-LnIII ions with two tartrates located in the center serving as “spokes”. Tb8 exhibits an extraordinary luminescence quantum yield (QYs) of 53.3% in the solid state under the excitation of 370 nm, while Eu8 cannot emit under similar conditions. Furthermore, Tb8 shows concentration-dependent emission in a methanol solution with the best luminescence QYl of 61.8%, representing one of the best luminescent Tb-based coordination clusters. The Eu ions can be rationally doped in the Tb ring (TbxEu8–x, 4 ≤ x < 8) by a stoichiometric ratio on specific sites to tune the emission color output, which reveals the efficient energy transfer from 5D4-7F5 and 5D4-7F6 levels of TbIII to the 5D0 level of EuIII. This work presents a unique method of controlling the fabrication and tunable luminescence of LCCs.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.