含有各種螢光染料之新穎性超分子材料其能量轉移行為的合成與研究

Abstract

本論文的核心目的是設計和建構含有各種螢光雙分子的新型超分子材料，用於探討與金屬離子，pH值，各種表面活性劑，光致變色，金屬離子等相互作用的能量轉移之有效條件及配體和主客相互作用。在介紹本博士論文時，我們早就描述了金屬超分子聚合物，主客體化學，聚集誘導放光（AIE）行為，光致變色，化學感應機理以及構建有效小或大能量轉移的基本嘗試和聚合材料以及可光切換材料。有趣的是，通過滿足能量分佈的要求來實現能量轉移，其中予體螢光團的發射光譜必須與受體螢光團的吸收光譜重疊。此外，還介紹了各種控制刺激下能量轉移材料的最新實例。另外，還詳細討論了相當罕見的單體放光TPE和銅和鐵金屬對羅丹明B衍生物的檢測。 本文透過採用TPE聚集誘導放光現象的有益效果，利用共價方法合成和構建了新的具有AlE效用的二元體材料具有RhB-TPE。其中，將羅丹明末端摻入Triton-X 100微胞中，研究了TPE自組裝能量調節的可行條件。接下來，我們構合成了一種新的共價AIE活性光可切換聚合物，二烯丙烯（DAE）和TPE單元的組合作為重複單元，以研究聚合物體系中DAE的開環和閉環形式之TPE的AIE行為。除共價方法探討能量調節外，我們還合成了含有金剛烷基（AD）客體和β-環糊精（β-CD）主體的雙FRET對的新型順序主客複合物（非共價方法），合成為與四苯醚乙烯（TPE）和羅丹明（RhB）客體以及BODIPY主體連接，BODIPY通過RhB在水介質中Fe3+金屬離子存在下的構型轉換行為來探測從TPE到RhB（開環態）的雙FRET現象。此外，本博士論文中，我們透過金屬配位和主-客相互作用合成了具有DAE-Terpyridine的線性控制光可切換和刺激響應超分子聚合物組合，以探究從三聯吡啶到DAE藉由光環化的能量轉移相關性質。 在第二章中，合成了由TPE和RhB單元的全新組合，組成的新穎雙色螢光材料TR-A和TR-B，透過pH變化和CH3CN各種水含量下的Cu2+相互作用來探討能量調節的最佳條件。有趣的是，TR-A和TR-B分別為60％和70％的水含量，有利於從TPE到RhB的最佳Cu2+介導的能量調節，從而實現游離RhB的最亮橙色放光，而且聚集誘發的放光完全消失（AIE）。此外，使用triton-X-100，SDS和CTAB的各種微胞條件來調節高含水量（分別為80％和90％）的TR-A和TR-B之能量調節。將RhB摻入triton-X-100微胞中，TPE破壞了AIE；因此，即使在有Cu2+ 離子的情況下也沒有發生從TPE到RhB的能量調節。有趣的是，陰離子表面活性劑（SDS）的微胞條件有利於在RhB附近增加Cu2+ 離子的局部濃度，並且透過亮橙色放光促進了原位生成非循環的游離RhB。 在第三章中，合成了重複單元中含有二芳基乙烯（DAE），四苯乙烯（TPE）和三唑接頭的新型可光切換聚合物P-PHT，並研究了TPE在開放狀態下的聚集誘導放光（AIE）行為並且在含水量高的P-PHT中形成DAE。在有機溶劑（THF），高含水量（90％H2O）和酸性條件下，P-PHT中DAE（從紫外線照射開環到閉環形式）的光切換現象顯著。在90％水含量下的P-PHT的UV照射，TPE的AIE從環化DAE的能量轉移完全淬息。有趣的是，TPE的罕見單體放光首先通過P-PHT中DAE的光環化發現，與PEDP中DAE開環形式的TPE的AIE行為在具有高含水量（90％ H2O）和酸性條件下相比。 在第四章中，合成了含有金剛烷基（AD）客體和β-環糊精（β-CD）主體的雙重FRET對的新型連續主客 - 複合物，與BODIPY主體連接四苯乙烯（TPE）和羅丹明（RhB）客體。重要的是，RhB在Fe3+ 離子存在下的構型切換行為經BODIPY在水性介質中促進了從TPE到RhB的雙重能量轉移現象。 在第五章中，我們透過有效的金屬配體和主客體相互作用設計和構建了一種新穎的線性光切換可控金屬超分子聚合物（Zn2+-TC/DS（開環和閉環）），其中二芳基乙烯單元連接通過配位Zn2+ 與雙三聯吡啶配位體構建了兩個二銨鹽基團和兩個二苯並-24-冠-8（DB24C8）臂，以研究經光環化從三聯吡啶到二芳基乙烯的能量轉移的相關性質即從藍色發射到青色）。此外，通過1H-NMR，UV / Vis和黏度測量驗證了線性光切換可控超分子聚合物Zn2+-TC/DS（開環和閉環）。可控制的超分子聚合物顯示出對不同pH和競爭性配體（亦即，環化）的多刺激響應能力。因此，這種自適應組裝和光切換可控金屬超分子聚合物的可逆複合過程提供了可用於構建可控分子開關的基本開/關機制。

The core objective of this dissertation is to design and construct the novel supramolecular materials containing various fluorescent dyads for the exploration of the hidden efficient conditions of energy transfer via means of interaction with metal ions, pH, various surfactants, Photo-chromism events, metal-ligand and host-guest interactions. In the introduction of this doctoral thesis we have described brief early the about the metallo-supramolecular polymers, host-guest chemistry, aggregation induced emission (AIE) behaviour, photochromism events, chemosensing mechanism and essential attempts to construct the efficient energy transfer based small or large and polymeric materials as well as photo-switchable materials. Delightfully, the energy transfer phenomea to be achieved by fulfill the requirement of energy profile, where the emission spectrum of the donor fluorophore must overlap with the absorption spectrum of the acceptor fluorophore. Furthermore, some latest examples of energy transfer based materials under various control stimuli were also introduced. In addition, the generation of quite rare monomeric emission of TPE and detection of copper and iron metal towards rhodamine B derivatives were also discussed in detail. Herein, by taking the fruitful benefit of aggregation induced emission phenomena of TPE, we have synthesized and constructed novel AIE active RhB-TPE-based dyad materials via covalent approach. In which, feasible conditions of energy modulations via self-assemblies of TPEs were explored by the incorporation of rhodamine terminal ends into Triton-X 100 micelles. In the continuation, we constructed a novel covalent AIE active photo-switchable polymer with a new combination of diarylethene (DAE) and TPE units as the repeating units to study the AIE behavior of TPE in both open and close form of DAE in polymeric system. Apart from covalent approach to explore the energy modulation event, we have also constructed novel sequential host-guest complexes (non-covalent approach) of dual FRET pairs containing adamantyl (AD) guests and β-cyclodextrin (β-CD) host were synthesized to link with tetraphenylethene (TPE) and rhodamine (RhB) guests along with BODIPY host for the exploration of dual FRET phenomena from TPE to RhB (open form) via BODIPY via conformational switching behaviour of RhB in the presence of Fe3+ metal ion in aqueous media. Furthermore, we have also constructed the novel DAE-Terpyridine-based linear controlled photo-switchable and stimuli-responsive supramolecular polymeric assembly via metal–ligand and host–guest interactions to explore the hidden associated properties of energy transfer from terpyridine to DAE by means of photo-cyclization events were comprised in this doctoral thesis as well. In chapter two, Novel bichromophoric materials TR-A and TR-B consisting of an entirely new combination of TPE and RhB units were developed to explore the optimum conditions of energy modulations via pH variation and Cu2+ interaction at various water contents of CH3CN. Interestingly, TR-A and TR-B, at 60 and 70% water contents, respectively, favored the optimum Cu2+-mediated energy modulations from TPE to RhB and thus achieve the brightest orange emissions of free RhB with complete disappearance of aggregation-induced emission (AIE) from TPE. Furthermore, various micellar conditions of triton-X-100, SDS, and CTAB were employed to adjust energy modulations of TR-A and TR-B at high water contents (at 80 and 90%, respectively). The incorporation of RhB into triton-X-100 micellar cavities disrupted AIE from TPE; thus, none of the energy modulations from TPE to RhB occurred even in the presence of Cu2+ ion. Interestingly, the micellar conditions of anionic surfactant (SDS) favored the increased local concentration of Cu2+ ions in the vicinity of scavangable RhB and facilitated the generation of noncyclic free RhB in situ via bright-orange emissions. In chapter three, a novel photo-switchable polymer P-PHT containing diarylethene (DAE), tetraphenylethene (TPE) moieties and a triazole linker in the repeating unit was synthesized to study the aggregation-induced emission (AIE) behaviour of TPE in both open and close forms of DAE in P-PHT with high water contents. The photo-switching phenomena of DAE (from open to close form under UV-irradiation) in P-PHT were prominent in organic solvent (THF), high water contents (at 90% H2O) and acidic conditions. Upon UV-irradiation of P-PHT at 90% water content, the AIE of TPE was completely quenched via energy transfer event from TPE to cyclized DAE. Interestingly, the rare monomeric emission of TPE was first discovered by the photo-cyclization of DAE in P-PHT compared with the AIE behaviour of TPE in the open form of DAE in P-PHT with AIE favourable conditions of high water contents (90% H2O) and acidic conditions. In chapter four, novel sequential host-guest complexes of dual FRET pairs containing adamantyl (AD) guests and β-cyclodextrin (β-CD) host were synthesized to link with tetraphenylethene (TPE) and rhodamine (RhB) guests along with BODIPY host. Importantly, the conformational switching behaviour of RhB in the presence of Fe3+ ion facilitated the dual energy transfer phenomena from TPE to RhB via BODIPY in aqueous media. In chapter five, We have designed and constructed a novel linear photo-swictahble controllable and stimuli-responsive supramolecular polymer Zn2+-TC/DS (open & close) via efficient metal-ligand and host-guest interactions, where the diarylethene unit linked two secondary ammonium salt groups and bearing two dibenzo-24-crown-8 (DB24C8) arms are constructed by coordinating Zn2+ with a bis-terpyridine ligand to explore the associate properties of energy transfer from terpyridine to DAE by means of photo-cyclization events. Moreover, the confirmation of demonstrated linear supramolecular polymer Zn2+-TC/DS (open & close) was further validated by 1H-NMR, UV/Vis spectra, PL spectra and specific viscosity measurements. The controllable and multi-stimuli responsiveness capabilities of host-guest and metal-ligand interactions in supramolecular polymer Zn2+-TC/DS (open & close) by means of interaction with different pH and a competitive chelating ligand (.i.e., cyclen) were studied.