開發在光電與生物應用中之碗烯基功能性材料

Abstract

作為一種非平面多苯環分子，碗烯可藉由有機合成方法進行官能化，用來製備多種功能性材料。本論文針對不同的應用開發了基於碗烯的功能性材料，包括電致變色/電致螢光變色薄膜、雙極電致變色超級電容器、近紅外光電致變色智能窗和活性氧光敏劑。在本論文中，這四種不同的應用將在四個部分中進行討論。 在第一部分中 π-共軛聚合物在電致變色材料研究中受到越來越多的關注，因為它們的顏色變化可以通過引入電子供體 (D) 和電子受體 (A) 部分而在很寬的範圍內改變。在這項研究中，我們合成了具有 D 和 A 部分的基於彎曲碗烯的單體，並將它們應用於製備π共軛聚合物以驅動顏色轉換。我們的共軛聚合物的吸收和發射特性可以通過將 D 和 A 部分插入共軛主鏈來調節。通過這項研究，已經證明基於碗烯的共軛聚合物具有穩定的電致變色特性和高光學對比度。此外，在這些聚合物中觀察到固態放光和可逆電致螢光轉換。這可能是由於在π共軛主鏈中加入非平面碗烯抑制了聚集誘導的猝滅。基於這些結果，我們認為嵌碗烯的π共軛聚合物是一種新的π共軛系統，具有多功能和可調的光學特性，可應用於現代光電器件。 第二部分描述了由五（N-烷基咔唑）-碗烯擴展紫精製成的雙極性聚合物用作電致變色超級電容器。具有可見能量存儲水平和高充電/放電速率的電致變色超級電容器已被用於為可穿戴和便攜式智能電子設備供電。具有氧化還原活性的π共軛聚合物受到了極大的關注，因為它們可以在摻雜/去摻雜過程中通過法拉第反應改變顏色並儲存能量。然而，由於供體和受體單元的共軛結構，用作電致變色超級電容器的共軛雙極性聚合物通常在中性和摻雜狀態下都會顯示顏色。作為非共軛連接鏈段的烷基接供體和受體單元，以幫助保留單個單元的電致變色行為，並追求透明到彩色的電致變色超級電容器。儘管如此，烷鏈長度仍會影響聚合物的光學對比度和比電容。具有丁基鏈作為連接基的雙極性聚合物在 p 摻雜和 n 摻雜區域分別顯示出最高的光學對比度和最佳的比電容性能(291 和 394 F g−1)。最後，雙極性聚合物被用於製造凝膠型電致變色器件，在充電/放電過程中展示了透明到綠色的轉換。 第三部分開發了碗烯-咔唑（CCZ）和3,4-乙烯二氧噻吩（EDOT）的共聚物薄膜並將其應用於近紅外電致變色窗。設計了兩種策略來提高近紅外電致變色性能，包括使用扭曲結構和共聚。 CCZ因其電聚合後的扭曲聚合物結構而被選為扭曲中心，與平面咔唑基材料相比，其表現出更好的近紅外電致變色性能，包括更快的響應和更高的穩定性。電化學阻抗分析表明，由於離子傳輸的增加，扭曲結構增強了近紅外電致變色性質。此外，採用共軛聚合物單體 EDOT 來提高近紅外區域的光學對比度。以不同的CCZ和EDOT投料比例製備了共聚物薄膜，並研究了這些共聚物的電化學性能和化學組成。最後，當使用合適的 EDOT 與 CCZ 比例時，共聚物薄膜可以表現出最高的光學對比度（1000 nm 下為 45%），這表明引入 EDOT 共聚可以進一步增強近紅外電致變色性。這項研究對用於電致變色應用的碗烯基材料的分子設計提供了重要的見解。 在第四部份中，碗烯在光照射下可產生有毒的活性氧物質，這在生物系統的疾病治療中具有潛在的應用。然而，目前還沒有有效的功能化策略可以同時賦予碗烯高水溶性和高效產生活性氧物質的能力。在此，提出了一種具有五個親水性旋轉基團的新型碗烯衍生物 (EGph-Cora)，可提高分子在水中的溶解度並減少其分子聚集。 EGph-Cora 表現出高光穩定性和 I 型和 II 型活性氧物質量子產率（分別為 0.2 和 0.99）。另一方面，碗狀的碗烯被認為有助於通過偶極-π-π相互作用進行自組裝。在玻璃基板上乾燥碗烯吡啶鹽後，觀察到有序結構是自組裝的良好跡象。

As a non-planar polycyclic aromatic hydrocarbon, corannulene was functionalized by organic synthesis to develop functional materials. The corannulene-based functional materials were developed for different applications in this dissertation, including electrochromic/electrofluorochromic films, ambipolar electrochromic supercapacitors, NIR electrochromic smart windows, and water-soluble corannulenes for ROS generation reagent and ionic liquid crystal. In this dissertation, these four different applications are discussed in four sections. In the first section, π-conjugated polymers have received increasing attention in electrochromic material research because their color change can be altered over a wide range by introducing electron-donor (D) and electron-acceptor (A) moieties. In this study, we have synthesized curved corannulene-based monomers with D and A moieties and applied them to prepare π-conjugated polymers to drive color switching. The absorption and emission properties of our conjugated polymers can be tuned by inserting D and A moieties into the conjugated backbone. Through this study, it has been demonstrated that corannulene-based conjugated polymers exhibit stable electrochromic properties with a high optical contrast ratio. Furthermore, emissions in the solid state and reversible electrofluorescence switching are observed in these polymers. This might be due to the inhibition of aggregation-induced quenching by incorporating nonplanar corannulene in the π-conjugated backbone. Based on these results, we consider corannulene-embedded π-conjugated polymers as a new π-conjugated system with versatile and tunable optical properties for application in modern optoelectronic devices. The second section describes ambipolar polymers made of penta(N-alkyl carbazole)-corannulene extended viologen for use as an electrochromic supercapacitor. Electrochromic supercapacitors with visible energy storage levels and high charge/discharge rates have been used to power wearable and portable intelligent electronics. Redox-active π-conjugated polymers have received significant attention because they can change color and store energy through a faradaic reaction during the doping/dedoping process. However, conjugated ambipolar polymers used as electrochromic supercapacitors generally display color at both neutral and doped states because of the extensive conjugation of the donor and acceptor units. The alkyl chain as a nonconjugated linker bridged the donor and acceptor units to help retain the electrochromic behaviors of the individual unit and pursue a transparent-to-color electrochromic supercapacitor. Still, the alkyl chain length affects the optical contrast and specific capacitance of the polymers. An ambipolar polymer with a butyl chain as a linker displays the highest optical contrast and the best performance of specific capacitance at 291 and 394 F g−1 in the p-doping and n-doping regions, respectively. Finally, the ambipolar polymer was applied to fabricate a gel-type electrochromic device, demonstrating a transparent-to-green switching during the charge/discharge process. The copolymer films of corannulene-carbazole (CCZ) and 3,4-ethylenedioxythiophene (EDOT) were developed and applied to near-infrared (NIR) electrochromic window in the third section. Two strategies were designed to improve the NIR electrochromic performance, including using a twisted structure and copolymerization. CCZ was selected as a twisted center due to its twisted polymer network after electropolymerization, which exhibited better NIR electrochromic performance, including faster response and higher stability, compared to planar carbazole-based materials. The electrochemical impedance analysis demonstrated the enhancing NIR electrochromism with the twisted structure originating from increasing ion transportation. In addition, EDOT, a monomer of a conjugated polymer, was employed to improve the optical contrast in the NIR region. The copolymer films were prepared in different feeding ratios of CCZ and EDOT, and the electrochemical properties and chemical composition of these copolymers were investigated. Finally, the copolymer films can exhibit the highest optical contrast (45% in 1000 nm) when a suitable ratio of EDOT to CCZ was used, indicating that introducing copolymerization with EDOT could further enhance the NIR electrochromism. This study gave critical insight into the molecular design of corannulene-based materials for electrochromic applications. In the fourth section, two types of water-soluble corannulenes were developed. First, corannulene produces toxic ROS under light irradiation, which has potential applications for disease treatment in biological systems. However, no effective functionalization strategy for endowing corannulene with high water solubility and efficient ROS production ability at the same time currently exists. Herein, a new corannulene derivative (EGph-Cora) with five hydrophilic rotating groups, which improve the solubility of the molecule in water and reduce its molecular aggregation, is presented. EGph-Cora exhibits high photostability and Type I and Type II ROS quantum yields (0.2 and 0.99, respectively). On the other hand, the bowl shape of corannulene was assumed to assist the self-assembly by dipolar π-π interaction. The order structure was observed as an excellent sign of self-assembly after drying the corannulene pyridinium salt on the glass substrate.