本研究設計並成功合成三個新穎的D-A’-π-A型無金屬有機染料分子（GH81、GH94與GH146），並與本實驗室先前所開發之染料EE174進行系統性的性能對比。此系列分子結構承襲本實驗室之設計策略，以2，6-位接有烷氧長碳鏈的三苯胺（Triphenylamine）為電子供體（Donor），並引進二苯基喹㗁啉（Diphenylquinoxaline）單元作為輔助受體（Auxiliary acceptor），其核心策略在於π共軛片段中引入不同的含氟芳香環結構與π單元，最後以氰基丙烯酸（Cyanoacrylic acid）作為電子受體與錨定基團。為了釐清不同π共軛片段對光伏表現之影響，本研究透過系統性的光物理、電化學與理論計算，探討結構對染料能隙、分子共平面性及電荷分離之調控，並藉由元件的電壓動力學分析（如IMVS），在標準模擬太陽光源下評估各染料之電荷傳輸與界面複合行為。實驗結果顯示，在I^-/I_3^-電解質系統下，GH81憑藉其最長的注入電子壽命與最顯著的TiO2導帶能階上移效應，展現出優異的光電轉換性能（Jsc = 15.60 mA cm-2， Voc = 0.76 V， η = 8.46%）。此外，本研究亦成功將此系列染料拓展至高電位鈷電解質與環保水相電解質系統中，並分別實現了顯著的性能突破（如GH81於鈷電解質下可達9.58%的優異效率，而GH94在水相電解質中亦可達7.62%的高效表現），完成了多重元件操作環境之應用探討。本研究之成果為高效率含氟有機敏化劑之分子結構設計提供了重要的理論依據與廣闊的應用前景。;In this study， three novel metal-free organic dyes (GH81， GH94， GH146) with a D-A’-π-A architecture were designed and successfully synthesized. A systematic performance comparison was conducted against EE174， a dye previously developed by our laboratory. Extending our laboratory’s previous molecular design strategies， these molecules feature a triphenylamine derivative substituted with long hydrophobic alkoxy chains at the 2，6-positions as the electron donor， and a diphenylquinoxaline moiety as the auxiliary acceptor. The core strategy of this work lies in the introduction of distinct fluorine-containing aromatic structures and customized π-units into the π-conjugated segment， with a cyanoacrylic acid group acting as both the electron acceptor and the anchoring group. To elucidate the intrinsic impact of these diverse π-conjugated segments on their photovoltaic performance， systematic photophysical， electrochemical， and theoretical calculations were conducted to investigate the structural modulation over energy gaps， molecular planarity， and charge separation properties. Furthermore， interfacial charge transport and recombination behaviors were comprehensively evaluated under standard simulated solar illumination via device dynamics analysis， such as intensity-modulated photovoltage spectroscopy (IMVS). Experimental results demonstrate that using the I^-/I_3^- electrolyte system， GH81 exhibits outstanding photovoltaic performance (Jsc = 15.60 mA cm-2， Voc = 0.76 V， η = 8.46%)， which is highly attributed to its prolonged injected electron lifetime and the most pronounced upward shift of the TiO2 conduction band edge. Additionally， this series of dyes was successfully extended to low-HOMO cobalt-based (Co^(2+/3+)) and eco-friendly water-based electrolyte systems， achieving significant performance breakthroughs under diverse operating environments， where GH81 reached a superior efficiency of 9.58% in the cobalt electrolyte， and GH94 yielded a high efficiency of 7.62% in the aqueous electrolyte. Overall， the outcomes of this study provide critical theoretical insights and promising application prospects for the structural design of high-efficiency fluorine-containing organic sensitizers.
