含Pyrene-Based化學感測材料、具有Diarylethene-Based光致開關高分子以及氟取代光伏高分子 之合成與研究

Abstract

本研究的主要目的是，合成新穎性的化學感測器對金屬離子和陰離子具有選擇性和靈敏性。在論文的介紹中我們描述了好幾種化學感測機制和超分子交互作用原理。許多化學感測文獻針對Al3+, Cr3+, Fe3+, Ag+, F- 和其他陽離子。我們已經開發新的pyrene-based Schiff base偵測探頭在半水性溶劑以及Hela細胞中完成了三價金屬離子的檢測。此外，我們也開發芘，蒽，萘，和苯懸吊imidazole探頭檢測F-。這些感測具有高選擇性和靈敏檢測可用肉眼和高度螢光鑑定，此外它們的蒽，萘系探針頭的靈敏性在OTFT設備可檢測到F-的存在。此外，我們開發了三個光可切換diarylethene-based旋光聚合物，其中RR和SS異構物在具有Ag+ 下其掌性單體可用圓二色儀檢測。除了感測的研究中，我們還研究了太陽能電池特性。在第五章中，我們設計並合成了四氟取代窄帶隙光伏共軛聚合物和鑑定其太陽能電池性能。 在第二章中，我們設計合成了新穎性pyrene-based螢光探頭FBP具有Schiff base和醯胺鍵作為受體，在紫外可見及螢光檢測下發現在不同的半水溶液條件對三價金屬離子具有選擇性。有趣的是，通過增加在FBP溶液 (DMSO / H2O) 的水含量，裡面的光致發光的聚集誘導放光比率 (AIREs) 會從藍色至綠色，是因為在水中的受激分子形成的聚集體而增強。此外，增強的聚合FBP的比例綠色螢光行為在半水性溶液及固態下，用以檢測在活細胞中的三價金屬離子(Al3+, Fe3+ 和Cr3+) 的存在都是很好的利用。更進一步驗證探頭檢測，他們對三價金屬離子的相互作用是用光譜回應的時間分辨光致發光 (TRPL) 以及理論計算上所驗證。因此，我們認為這樣一個新的AIRE-based的應用在Schiff base 和 pyrene-based螢光化學感測和生物感測是第一次被報導。 在第三章中，我們展示了一系列的pyrene-, anthracene-, naphthalene- 及 benzene-appended imidazole-based 探頭 (分別為 IMP， IMA，IMN 和 IMB)，用了一種簡單的單合成步驟，合出了選氟離子具有選擇性的螢光檢測 。在這些探頭中， IMP具有最好的感測性和選擇性。在分子內電荷轉移 (ICT) 的相互作用和與氟離子鍵結機制通過光致發光 (PL) 和1H -NMR是很容易被鑑定和正名。更重要的是，通過有機薄膜電晶體 (OTFT) 和表面形態學來鑑定imidazole-based的衍生物對於氟化物的檢測也是一種新的方式。因此， F-檢測在溶液中和固體形式可以透過3種信號源來鑑定，肉眼和PL觀察顏色變化以及OTFT元件的截止電流值。 在第四章中，我們設計和合出旋光高分子 (C-SSP, C-RRP, and C-RSP) 具有光致變色bis-thienylethene單元在主鏈上。旋光高分子透過光環化和非光環化來檢驗它們傑出光開關，藉由透過 bis-thienylethene 各自的放光輻射。光致開關由於旋性的調整這類的旋光信號可以通過與金屬離子的相互作用得到進一步調整。因此用或不用金屬離子皆得到的旋光調整。SS 和 RR 中心的聚合物所得到的圓二色信號被完全相反，而在RS-中心聚合物圓二色信號是平的。非環化的聚合物 (O-SSP, O-RRP, and O-RSP) 由於具有柔軟的bis-thienylethene單元，因此對金屬離子的交互作用不顯著 ，相較之下，環化聚合物(C-SSP, C-RRP, and C-RSP) 具有剛性的bis-thienylethene對金屬離子的交互作用較佳。通過可逆的光致開關和金屬離子的相互作用來調整旋光是非常罕見的。 在第五章中，我們使用的Stille 縮合聚合來合成一系列的低能隙氟取代的共軛聚合物含有電子予體benzodithiophene (BDT) 和電子受體quinoxaline (Qx) 單元，後者具有兩個或四個氟原子。這些供體/受體聚合物顯示出一個寬吸收範圍 (從300至750奈米)，具有低於1.20電子伏特的帶隙能量 (使用循環伏安法測得)。因為thiophene單元是強烈電子予體，供體/受體的聚合物中具有更高度氟化的結構擁有的最低帶隙 (低至1.14電子伏特)。因此，誘導的這些測試聚合物中的最大光電轉換性能。高分子太陽能電池具有的聚合物PTF2的活性層用PC70BM共混 (1：1.5，W / W) 可得到的最高功率轉換效率 (2.13％)，同時具有短路電流密度8.7 mA cm–2，開路電壓0.72 V，和填補因子0.34。

Mainly in this study is to synthesize novel chemosensor materials for selective and sensitive detection of metal ions and anions. In the introduction of the thesis we have described about several chemosensing mechanisms and the concepts of supramolecular interactions. Many sensor probes were reported for Al3+, Cr3+, Fe3+, Ag+ and F- cations and anion, respectively. Herein, we have developed and established novel pyrene-based Schiff base sensor probes for trivalent metal ion detections in samiaquous solvents as well as their detection in Hela-cells. Moreover, we developed pyrene, anthracene, naphthalene, and benzene appended imidazole probes for F- ion detections. They are naked eye and highly fluorescent selective and sensitive detectable as well as their anthracene, naphthalene-based probes are sensitively detected in OTFT devices also in presence of F- ion. In addition, we developed three photo-switchable diarylethene-based chiral polymers, where RR and SS isomers are CD active and used to tune their chirality in presence of Ag+ ion with their monomers. Apart from the sensor studies, we also studied the solar cell in fifth chapter. Herein, we designed and synthesized four fluoride-substituted narrow band-gap conjugated photovoltaic polymers and characterized their solar cell performances. In the second chapter, we synthesize a newly designed pyrene-based fluorescent probe FBP containing a Schiff base and amide linkage as a receptor, which demonstrates selective UV-visible and fluorometric detections of trivalent metal ions in various semi-aqueous solution conditions. Interestingly, by increasing water contents the aggregation induced ratiometric emissions (AIREs) of photoluminescence in FBP solutions (in DMSO/H2O) are enhanced from blue to green due to the excimer formation of the aggregates in water. In addition, the enhanced aggregated ratiometric green fluorescence behaviors of FBP in the presence of trivalent metal ions (Al3+, Fe3+, and Cr3+) are observed in semi-aqueous solutions as well as the solid state, which is well utilized to detect trivalent metal ions in living cells. Further verification of the probe detections, their interactions towards trivalent metal ions are well characterized by the time-resolved photoluminescence (TRPL) of spectroscopic responses as well as theoretical calculations. Therefore, we believe the application of such a new AIRE-based approach is first reported among Schiff base and pyrene-based fluorescent chemo- and bio-sensors. In the third chapter, we demonstrate a series of pyrene-, anthracene-, naphthalene- and benzene-appended imidazole-based probes (IMP, IMA, IMN and IMB, respectively), in a facile fashion of single synthetic step, for the selective colorometric and fluorometric detections of fluoride ion ratiometrically. Among these probes, IMP revealed the best sensor capability and selectivity. The intramolecular charge transfer (ICT) interactions and binding mechanisms with fluoride ion were well characterized and proven through photoluminescence (PL) and 1H-NMR titrations. More importantly, prevailing fluoride detections by organic thin film transistors (OTFTs) and morphological characterizations of imidazole-based derivatives are also demonstrated in a new way. Therefore, F− detection could be completed by three kinds of signal sources in the form of color changes by the naked eye and PL observations as well as the off-current values of OTFT devices in their solution and solid forms. In the fourth chapter, we demonstrate the design and construction of chiral (C-SSP, C-RRP, and C-RSP) polymers bearing photochromic bis-thienylethene unit in the main chain. Constructed chiral polymers were examined for their eminent photo-switching through the photo-cyclization and non-photo-cyclization events of bis-thienylethene unit through their respective irradiations of light. Photo-switching resulted chiral tuning and such chiral signal could be further tuned by the interaction with metal ion. Therefore chiral tuning were obtained with or without metal ions. The obtained CD signals were completely reverse to each other for SS and RR-center-based polymers and almost complete CD silent for RS-center-based polymer. Non-cyclized polymers (O-SSP, O-RRP, and O-RSP) due to their flexible bis-thienylethene unit were less effective towards the interaction of metal ion as compared to cyclized polymers (C-SSP, C-RRP, and C-RSP) having rigid bis-thienylethene unit. Significant chiral tuning through reversible photo-switching and by means of metal ion interactions are very rare. In the fifth chapter, we used Stille polycondensation to synthesize a series of low–band gap fluoride-substituted conjugated polymers containing electron-donating benzodithiophene (BDT) and electron-accepting quinoxaline (Qx) units, with the latter presenting either two or four fluoride atoms. These donor/acceptor polymers exhibited a broad absorption range (from 300 to 750 nm), with band gap energies of less than 1.20 eV (measured using cyclic voltammetry). Because of their strongly electron-donating thiophene units, the donor/acceptor polymers featuring the more highly fluorinated structures possessed the lowest band gaps (as low as 1.14 eV) and, thus, induced the greatest photovoltaic performance among these tested polymers. The highest power conversion efficiency (2.13%) was obtained from the polymer solar cell featuring an active layer of the polymer PTF2 blended with PC70BM (1:1.5, w/w), with a short-circuit current density, open circuit voltage, and fill factor of 8.7 mA cm–2, 0.72 V, and 0.34, respectively.