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一系列含一维手性LnO(Ln = Eu、Tb、Sm、Dy)链的镧系-喹喔啉-2,3(1,4)-二酮配合物:发光性质及对小分子的响应

A series of lanthanide-quinoxaline-2,3(1,4)-dione complexes containing 1D chiral LnO (Ln = Eu, Tb, Sm, Dy) chains: luminescent properties and response to small molecules.

作者信息

Hassan Sadaf Ul, Farid Muhammad Asim, Wang Yingxia

机构信息

University of Management & Technology Lahore campus Lahore 54770 Pakistan.

COMSATS University Islamabad (CUI) Lahore Campus Lahore 54000 Pakistan

出版信息

RSC Adv. 2021 Oct 29;11(53):33309-33318. doi: 10.1039/d1ra05719g. eCollection 2021 Oct 8.

Abstract

Five new isostructural lanthanide-organic complexes, [LnO(OH)(HQXD)(HQXD)]·HO (Ln = Eu 1, Tb 2, Sm 3 Dy 4 and Gd 5; HQXD = quinoxaline-2,3(1,4)-dione), have been synthesized under hydrothermal conditions. These complexes are characterized by powder X-ray diffraction (PXRD), infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric-differential thermal analysis (TG-DTA) and photo-luminescent spectroscopy. Single crystal X-ray diffraction analysis of complex 1 revealed that the structure featured in 1D chiral "EuO" chains surrounded by coordinating organic ligands. These chains are interconnected hydrogen bonding and offset π⋯π stacking interactions of the ligands to form the 3D supramolecular frameworks. The photo-luminescence studies for complexes 1-5 disclosed that the ligand (HQXD) showed an antenna effect to transfer energy toward the lanthanide cations. The energy transfer mechanism investigations show that the energy transition from the triplet energy level (ππ*) of ligand HQXD to the Tb cation is more effective than to the Eu, Sm and Dy ions; therefore it has been selected as a representative to examine the potential for sensing small molecules. Complex 2', which was obtained by the heating treatment of 2 at 150 °C, displayed a high luminescence sensitivity towards small solvent molecules. Tertiary butanol (-butanol) was found to be an excellent sensitizer, while tetrahydrofuran (THF) was a highly quenching species. Complex 2' could regain a higher photo-luminescence intensity after treating for 5 cycles with -butanol, revealing a prospect for reusability.

摘要

在水热条件下合成了五种新的同构镧系有机配合物,[LnO(OH)(HQXD)(HQXD)]·H₂O(Ln = Eu 1、Tb 2、Sm 3、Dy 4和Gd 5;HQXD = 喹喔啉-2,3(1,4)-二酮)。通过粉末X射线衍射(PXRD)、红外光谱(IR)、元素分析(EA)、热重-差热分析(TG-DTA)和光致发光光谱对这些配合物进行了表征。配合物1的单晶X射线衍射分析表明,其结构特征为一维手性“EuO”链,周围环绕着配位有机配体。这些链通过氢键和配体的错位π⋯π堆积相互作用相互连接,形成三维超分子框架。对配合物1 - 5的光致发光研究表明,配体(HQXD)表现出天线效应,将能量转移到镧系阳离子上。能量转移机制研究表明,从配体HQXD的三重态能级(ππ*)到Tb阳离子的能量转移比到Eu、Sm和Dy离子更有效;因此,它被选为检测小分子潜力的代表。通过在150℃下对2进行热处理得到的配合物2',对小溶剂分子表现出高发光灵敏度。发现叔丁醇(-丁醇)是一种优异的敏化剂,而四氢呋喃(THF)是一种高度猝灭物质。配合物2'在用-丁醇处理5个循环后可以恢复更高的光致发光强度,显示出可重复使用的前景。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7785/9044319/7369db27ec79/d1ra05719g-f1.jpg

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