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標題: | 烷基鏈長效應對蒽-五苯荑衍生物之光致機械力放光變色之探究 Alkyl Chain Length Effects on the Photomechanochromic Luminescence of Anthracene-Pentiptycene Derivatives |
作者: | Cheng-Zong Kuo 郭承宗 |
指導教授: | 楊吉水 |
關鍵字: | 五苯荑,烷基鏈長效應,光致機械力放光變色, Pentiptycene,Alkyl chain length effect,Photomechanochromic Luminescence, |
出版年 : | 2019 |
學位: | 碩士 |
摘要: | 智能材料是利用化合物對外在刺激 (外力、蒸氣、光照、熱源等) 具有響應,而產生可被偵測的變化量。近年來,以光作為刺激源的放光智能材料逐漸嶄露頭角。本實驗室近年發展了結合單邊的五苯荑,並以蒽作為螢光團的化合物 1-AnP (C8),其於固態下展現了同質多形性。而從此二型晶體結構得知,分子對雙雙分別呈現兩種型態:一為蒽與蒽排列較緊密,且符合拓撲化學有利進行 [4+4] 二聚作用的Y型;及蒽與蒽排列較不緊密,不符合 [4+4] 二聚作用的拓撲化學結構之G型。而在光刺激下,Y型與G型卻皆會進行二聚作用,且展現著兩種迥然有別的放光變色行為,為文獻中前所未見的光致機械力放光變色 (photomechanochromic luminescence, PMCL) 現象。
從Y型及G型的單晶繞射結構得知,末端烷基碳鏈與五苯荑間具有交互作用。因此,本論文藉由調控1-AnP (C8) 的末端烷基碳鏈長度,設計出1-AnP (Cn) 的系列化合物,分別利用再沉澱的技巧得到具同質多晶型性的對於Y型、G型及B型樣品。我們分別對此三種型態進行PMCL性質的探討,並進而比較各型中的放光行為變化與鏈長效應的關聯性。其中,本論文對於G型在光刺激下,不同鏈長所展現的的不同PMCL性質,以晶體結構、光物理參數及其他實驗數據詳加探討,進而提出模型來解釋其變色的機制。經由合成1-AnP (Cn) 的系列分子,期許鏈長效應可對於日後科學家對於固態螢光材料的分子設計上,及對於光致機械力放光變色的性質,得以提供更多的見解及描述。 Smart luminescent materials are those responsive to external stimuli, such as external force, vapor, light exposure and heat treatment, and can further produce measurable variation. Among them, light-induced smart materials have received considerable attention. In our previous work, we have synthesized 1-AnP (C8), a monosubstituted anthracene as the chromophore with pentiptycene moiety. It shows two polymorphs in the solid state. From the crystal structures of the two polymorphs, they show two types of molecular pairs respectively. One of them shows stronger anthracene-anthracene interactions and leads to yellow fluorescence (Y form) and another polymorph shows weaker anthracene-anthracene interaction and corresponds to green fluorescene (G form). The anthracene-anthracene geometry in the Y form conforms to the topochemically favorable [4+4] photodimerization structure, but that in the G form is relatively unfavorable for [4+4] photodimerization. However, both of them can undergo [4+4] photodimerization and show distinct fluorescence color change due to photomechanical force. We called it “photomechanochromic luminescence”, abbreviated as PMCL. From the crystal structures of the Y form and G form, they both show the interaction between pentiptycene moiety and terminal alkyl chain. Therefore, we designed the 1-AnP (Cn) derivatives with different length of terminal alkyl chain. And we could get the polymorphic yellow, green, and blue form by reprecipitation. We carried out the tests on the PMCL properties of three polymorphs and further compared the relevance between the fluorescence and alkyl chain length effect. Among them, we emphasized different PMCL properties of G form with distinct length of alkyl chain by looking deep into the crystal structures, photophysical properties and other experimental data and proposed the mechanism to explain the fluorescence color change. By synthesizing a series of 1-AnP (Cn) derivatives, we hope the alkyl chain length effect can pave the way for the molecular design of the solid state fluorescent materials and the better understanding of the PMCL properties. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77189 |
DOI: | 10.6342/NTU201903857 |
全文授權: | 未授權 |
顯示於系所單位: | 化學系 |
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