Design of Near-Infrared Luminescent Lanthanide Complexes Sensitive to Environmental Stimulus through Rationally Tuning the Secondary Coordination Sphere
文献类型：期刊论文
| 作者 | Ning, Yingying; Liu, Yi-Wei; Meng, Yin-Shan; Zhang, Jun-Long |
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2018-02-05 |
| 卷号 | 57期号:3页码:1332-1341 |
| ISSN号 | 0020-1669 |
| DOI | 10.1021/acs.inorgchem.7b02750 |
| 英文摘要 | The design of near-infrared (NIR) emissive lanthanide (Ln) complexes sensitive to external stimulus is fundamentally important for the practical application of Ln materials. Because NIR emission from Ln is extremely sensitive to X-H (X = C, N and O) bond vibration, we herein report to harness the secondary coordination sphere to design NIR luminescent lanthanide sensors. Toward this goal, we designed and synthesized two isomeric [(eta(5)-C5H5)Co{(D3CO)(2)P = O}(3)]-Yb(III)-7,8,12,13,17,18-hexafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porpholactol NIR emitters, Yb-up and Yb-down, based on the stereoisomerism of porphyrin peripheral beta-hydroxyl group. Yb-up, in which beta-OH is at the same side of Yb(III) center, can form an intramolecular hydrogen bond with the axial Klaui ligand, whereas Yb-down cannot because its beta-OH is opposite to Yb(III) center. X-ray crystal structures and photophysical studies suggested that the intramolecular hydrogen bond plays important roles on the NIR luminescence of ytterbium(III), which shortens the distance between beta-OH and Yb(III) and facilitates the nonradiative deactivation of Ln excited state. Importantly, Yb-up/down were demonstrated to be highly sensitive toward temperature and viscosity. The PMMA polymer using Yb-up as the dopant NIR emitter showed thermosensitivity up to 6.0% degrees C-1 in the wide temperature range of 77-400 K, higher than that of Yb-down (3.8% degrees C-1). These complexes were also explored as the first NIR viscosity sensor, revealing their potential applications as optical sensors without visible light interference. This work demonstrates the importance of secondary coordination sphere on designing NIR Ln luminescent functional materials. |
| 语种 | 英语 |
| WOS记录号 | WOS:000424730800046 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/45731]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Zhang, Jun-Long |
| 作者单位 | Peking Univ, Beijing Natl Lab Mol Sci, Coll Chem & Mol Engn, State Key Lab Rare Earth Mat Chem & Applicat, Beijing 100871, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ning, Yingying,Liu, Yi-Wei,Meng, Yin-Shan,et al. Design of Near-Infrared Luminescent Lanthanide Complexes Sensitive to Environmental Stimulus through Rationally Tuning the Secondary Coordination Sphere[J]. INORGANIC CHEMISTRY,2018,57(3):1332-1341. |
| APA | Ning, Yingying,Liu, Yi-Wei,Meng, Yin-Shan,&Zhang, Jun-Long.(2018).Design of Near-Infrared Luminescent Lanthanide Complexes Sensitive to Environmental Stimulus through Rationally Tuning the Secondary Coordination Sphere.INORGANIC CHEMISTRY,57(3),1332-1341. |
| MLA | Ning, Yingying,et al."Design of Near-Infrared Luminescent Lanthanide Complexes Sensitive to Environmental Stimulus through Rationally Tuning the Secondary Coordination Sphere".INORGANIC CHEMISTRY 57.3(2018):1332-1341. |
入库方式： OAI收割
来源：化学研究所
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