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    题名: 含三價釤離子配位聚合物內淬熄效應之研究
    作者: 温書涵;Wen,Shu-Han
    贡献者: 化學學系
    关键词: 稀土元素;釤離子之淬熄效應
    日期: 2016-07-26
    上传时间: 2016-10-13 12:44:32 (UTC+8)
    出版者: 國立中央大學
    摘要: 本論文以中溫水熱法合成以1,4-cyclohexanedicarboxylate (C8H10O4, 簡稱CHDC)作為配位基含有不同莫耳比例稀土元素之R2(CHDC)3 (R= Y, Tb, Sm) 配位聚合物。這些聚合物皆以單晶及粉末X光繞射實驗去鑑定晶體的結構與純度,並以感應耦合電漿原子發射光譜分析儀(ICP-AES)鑑定配位中心之元素比例。在含三價釤離子(trivalent samarium)的配位聚合物光譜中,我們觀測到複雜的淬熄現象(quenching phenomena)。針對這些不同稀土元素比例之配位聚合物,我們取得完整之光致放光光譜(photoluminescence spectra)、激發光譜(excitation spectra)及時間解析光譜(time-resolved spectra),並藉由分析這些光譜資料,我們成功地以動力學模型去解釋在這些配位聚合物中的淬熄現象,並取得完整的相關速率常數。由分析結果得知其中存在兩種淬熄機制,第一種是在YxSmyTb2-x-y(CHDC)3化合物中,淬熄是與Sm3+與Tb3+的濃度無關;另一種則是在SmxTb2-x(CHDC)3化合物中,淬熄是與Sm3+濃度成正比關係。另外,使用光源355 nm激發時得到的各個化合物淬熄速率都較使用光源303.5 nm時大,顯示以355 nm激發時淬熄效應較為嚴重。;Coordination polymers, R2(C8H10O4)3, with 1,4-cyclohexanedicarboxylate (C8H10O4, CHDC) ligands and different compositions of rare earth elements (R= Y, Tb, and Sm) were synthesized by mid-temperature hydrothermal method. Single crystal and powder x-ray diffraction (XRD) data of these compounds were acquired for confirming their structure and purity. Inductively Coupled Plasma Atomic Emission Spectra (ICP-AES) were also obtained to verify the compositions of rare earth elements. In the spectra of coordination polymers containing trivalent samarium (Sm3+), complicated quenching phenomena were observed. For these coordination polymers, photoluminescence (PL), excitation, and time-resolved spectra were recorded. Kinetics models were adopted for analyzing the spectral data. There exist two quenching mechanisms. For YxSmyTb2-x-y(CHDC)3, the quenching rate is irrelevant to the Sm3+ concentration, whereas for SmxTb2-x(CHDC)3, the quenching rate is proportional to the Sm3+ concentration. The results can successfully explain the observed quenching phenomena, and complete quenching rate constants were determined.
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