光開關及多重化學刺激響應之超分子高分子

Abstract

本篇碩士論文中成功發表新型光開關及多重化學刺激響應之金屬超分子高分子合成及其性質表徵，此高分子藉由金屬配位與主客化學兩種超分子作用力自組裝而成，其單體結構為(terpyridineyl-DB24C8)分子作為主體與光開關衍生物(DAEs)作為客體(主:客=2:1)建構而成之準輪烷單體，準輪烷單體間透過鋅離子配位自組裝成超分子高分子(主:客:鋅 = 2:1:1)，在可見/紫外光照射下，高分子可轉化為開/關組態，其中高分子(關)可成功將鋅-環之螢光能量轉移至DAEs(關環組態)上，螢光強度大幅上升並有明顯顏色改變。這種新穎超分子高分子可藉由鋅離子除去/導入達到分離/自組裝準輪烷單體；以及鹼/酸性刺激可使主客體分離/自組裝，可逆的超分子作用力亦造成其螢光放射強度及波長位移之可逆現象，金屬離子及酸鹼刺激響應行為在紫外/可見光譜、螢光光譜及1H NMR光譜中均獲得證實，而濃度變化之1H NMR光譜及黏度量測結果更進一步證實了線性高分子的形成。 本團隊新穎想法與設計成功的應用了二芳基乙烯之光致變色基團，超分子高分子藉由能量轉移機制將螢光由深藍色轉化為天空藍，不僅可由肉眼觀察其明顯顏色改變，其螢光強度亦大幅增強，本篇研究提供了一個新的概念來開發智能超分子聚合材料未來有機會被應用在金屬、光及酸鹼度等感測器。

In this master thesis, we presented a novel photochromic metallosupramolecular polymer synthesis scheme and properties characterization. The supramolecular polymer self-assembled by metal-ligand coordination and host-guest interactions of pseudorotaxane. The supramolecular polymer was self-assembled by molar ratio = 2:1:1 mixing complex of terpyridine functionalized dibenzo-24-crown-8 (DB24C8) derivatives (5), Zinc ion (Zn2+) and diarylethene-containing ammonium salt (10). Thanks to fluorescence resonance energy transferred from terpyridine to DAE salt, the polymer solution exhibited appreciable emission change either with UV/Vis irradiation or multi-chemical stimulation. The metal-ligand coordination and host-guest interactions can be reversible in the presence of Zn2+/cyclen and base/acid, respectively. Investigations on chemical multi-stimuli response of supramolecular polymer were monitored by UV-Vis, photoluminescence and 1H NMR spectrum. The formation of linear polymer is also evidenced by 1H NMR spectrum and viscosity measurement. This new supramolecular polymer utilized DAE photochromic behavior which changed the metal-terpyridinylmacrocycle fluorescence from deep blue to skyblue, including intensity enhancement and wavelength shift. Meanwhile, we have developed facile photochromic switchable supramolecular polymer that have potential for further applications such as metal, light or pH sensors.