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博碩士論文 etd-0711103-114929 詳細資訊
Title page for etd-0711103-114929
論文名稱
Title
1.四萘甲基取代雙二茂鐵混價化合物分子內電子傳遞之研磨效應 2.含叁吡啶取代基之雙二茂鐵化合物之合成與其在分子導線之應用
1. Pronounced Effects of Grinding on Rates of Intramolecular Electron Transfer in Tetranaphthylmethyl Substituted Mixed- Valence Biferrocenium Triiodide. 2. The Application of Terpyridinyl Substituted Biferrocene Complexes in the Development of Molecular Wires: Preparations and Characterization.
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
226
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2003-06-25
繳交日期
Date of Submission
2003-07-11
關鍵字
Keywords
雙二茂鐵、分子導線、電子傳遞、叁
electron transfer, terpyridinyl, biferrocene, molecular wires
統計
Statistics
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The thesis/dissertation has been browsed 5685 times, has been downloaded 2311 times.
中文摘要
本文第一章主要在探討化合物1.34、1.35 (1', 2', 1', 2'-tetranaphthylmethyl- and 1', 3', 1', 3'-tetranaphthylmethyl- biferrocenium triiodide)的分子內電子傳遞的現象。本文利用梅思堡光譜、電子順磁共振光譜與X光粉末繞射等光譜對此兩個化合物進行不同的製備方式與樣品研磨前後的電子傳遞測量,發現在此兩個化合物的晶體樣品(crystalline,方法二)中,有明顯的研磨效應;即其分子內電子傳遞速率皆會從大於梅思導光譜轉變為小於梅思堡光譜的偵測極限(~107 / sec),經過電子順磁共振光譜與X光粉末繞射的佐證,我們推測這是因為施以物理性質的研磨造成晶體樣品中的結構改變因而導致分子內電子傳遞速率的大幅度減緩。
第二章所要闡述的是以雙二茂鐵分子為連接單位的雙叁
Abstract
Ch1
The X-ray structural determinations of the neutral 1',2',1'",2'"-tetranaphthylmethyl- and the 1', 3', 1', 3'-tetranaphthylmethyl- biferrocenium triiodide have been determined. Our Mossbauer measurement for 1.34 and 1.35 indicate that the intramolecular electron transfer rates are quite sensitive to the environmental perturbations caused by the grinding of the sample. An interesting finding is that the Mossbauer results indicate that the unground diffusing sample of 1.34 is valence delocalized on the Mossbauer time scale above 180K. However, the ground diffusing sample of 1.34 exhibits a Mossbauer spectrum characteristic of a valence-trapped cation which remains valence-trapped electronic state at 300K. The effects of grinding of samples are also observed in the EPR and XRD measurements.
Ch2
A great deal of research has concentrated on long range electron and energy transport in transition metal- based system and conducting polymer. We have synthesis a new bis-terpyridine bridging ligand (2.40) which the spacer is biferrocene moiety. Incorporating of the Ruthenium (II) subunits via redox-active spacer group promote to construction polynuclear transition metal complexes (i.e. multicomponent system). Cyclic voltammetric analysis indicated that there are Fe-Fe electronic coupling in the bridging ligand, and the degree of Fe-Ru electronic coupling is weak. In addition to dominant UV absorption near 240 and 280 nm from terpyridinyl and MLCT absorption from Ru to terpyridine around 480 nm, the complexes containing ferrocene or biferrocene as endgroup exhibit an unusual absorption band around 560 nm which is due to a feccocene moiety to terpyridine MLCT transition.
目次 Table of Contents
目錄
目錄……………………………………………………………. i
圖目錄 ………………………………………………………….v
表目錄 ……………………………………………………….viii
附錄 …………………………………………………………..ix




第壹章 四萘甲基取代雙核二茂鐵衍生物的電子傳遞

1-1 前言 ………………………………………………………1
1-1-1 混合價位化合物之定義與類別 ……………………1
1-1-2 混合價位化合物之理論探討 ……………………….5
1-1-3 混合價位化合物的電子傳遞速率測量 …………….8
1-1-4 影響固態電子傳遞速率的因素 …………………...11
1-1-5 研究目的 …………………………………………...29

1-2 實驗
1-2-1 藥品部份 …………………………………………...37
1-2-2 儀器部份與物性測量的方法 …………………….37
1-2-3 樣品的製備 ………………………………………..38


1-3 結果與討論
1-3-1 57Fe 梅思堡光譜的特性 …………………………...40
1-3-2 電子順磁共振光譜的探討 ………………………..60
1-3-3 粉末繞射圖的探討 ………………………………...65

1-4 結論 …………………………………………………….68

1-5 參考文獻 ………………………………………………..70

第貳章 含叁
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