| 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. |
