新型含螺吡喃和萘并哌喃的 光致變色釕錯合物染料之合成探討

Please use this identifier to cite or link to this item: https://ir.lib.ncu.edu.tw/handle/987654321/97586

Title:	新型含螺吡喃和萘并哌喃的光致變色釕錯合物染料之合成探討
Authors:	王道融;Wang, Dao-Rong
Contributors:	化學學系
Keywords:	釕錯合物染料;光致變色;ruthenium complex;photochromic
Date:	2025-08-26
Issue Date:	2025-10-17 11:38:57 (UTC+8)
Publisher:	國立中央大學
Abstract:	光致變色材料是可透過照光產生顏色變化，但在染料敏化太陽能電池(DSCs)研究領域中，僅有極為稀少的全有機光致變色染料研發成果，因此本研究希望以釕錯合物M1 ([Ru(dcbpy)2 (dmbpy)]·2(PF6))作為分子基礎架構，合成出兩個新型光致變色釕錯合物(CYC-62及 CYC-64)，使用兩個dcbpy作為固著配位phen與dmbpy輔助配位基上分別連接spiropyran 和 naphthopyran光致變色單元，並將其配位至釕金屬，探討中心金屬對這些光致變色單元的光致變色特性的影響。本研究使用三種合成方法(Vilsmeier-Haack ， Reimer-Tiemann ， Duff reactions)進行CHO-OH phen的合成，發現前述兩種方法，會因為無法有效率地將在5號位接上醛基，而導致結構不正確(CHO-OH phen-V) 或是產率過低(CHO-OH phen-R)，最後使用Duff reaction能有效地解決前述所遇到的問題。透過1H-NMR光譜圖和吸收光譜圖發現L62在溶液中會同時具有開合環結構，且因應溶劑的種類和濃度使其開合環比例也會有所變化。將光致變色單元配位至釕金屬使用三種不同的合成方法，方法一的結果證明光致變色單元結構熱穩定性不佳，會在長時間高溫攪拌(> 36 h，> 80 oC)後失去光致變色特性，方法二則是先合成 [Ru(dmbrbpy)(dmcbpy)2]2+再將naphthopyran與其進行反應，但在合成過程中發現dmbrbpy因熱穩定性不佳而形成[Ru(dmcbpy)2(dmOHbpy)]2+，進而使後續naphthopyran無法發生反應，最後方法三導入AgNO3，透過先將Ru(dmcbpy)2Cl2的Cl-脫去，可降低配位溫度再將 L62 和L64進行配位得到CYC-62 ester和CYC-64 ester，後續透過水解反應得到目標產物CYC-62和CYC-64。透過1H-NMR光譜圖發現L62的光致變色單元 spiropyran 配位至釕金屬後，會從同時具有開合環結構(C/O = 1/0.6，DMSO-d6 )轉變為幾乎為開環結構(C/O : (0.08/1) )，而 L64的光致變色單元naphthopyran 與 spiropyran 不同，在配位至釕金屬後則仍會維持合環結構。;Photochromic materials can change colors after light irradiation. However, so far, there are only very few fully organic photochromic dyes developed in the field of dye-sensitized solar cells (DSCs). Therefore, this study hopes to use the ruthenium complex M1 ([Ru(dcbpy)2(dmbpy)]2(PF6)) as the molecular framework to synthesize two new photochromic ruthenium complexes (CYC-62 and CYC-64). The molecular design uses two dcbpy as the anchoring ligands. Using phen and dmbpy, respectively, connects the spiropyran and naphthopyran photochromic units as the ancillary ligands and coordinates them to the ruthenium metal. The influence of the central metal on the photochromic properties of these photochromic units is also explored to provide new directions for molecular design. Three synthetic methods (Vilsmeier-Haack, Reimer-Tiemann, and Duff reactions) were used to synthesize CHO-OH phen. It was found that the structures of CHO-OH phen synthesized by Vilsmeier-Haack and Reimer-Tiemann reactions were either incorrect or had low yields due to inefficient aldehyde attachment at the 5-position. Finally, the use of the Duff reaction can effectively solve the problems encountered by the above two methods. Through ¹H-NMR and absorption spectrum, it was found that L62 exists in both opened and closed-ring forms in solution, the ratio of opened/closed ring varying by solvent and concetration. Three methods were used to coordinate the photochromic units to the ruthenium metal. Method 1 indicates that the photochromic unit has poor thermal stability, undergoing structural changes and losing photochromic properties after prolonged (>36 h, >80 °C). Method 2 is to first synthesize [Ru(dmbrbpy)(dmcbpy)2]2+ and then react naphthopyran. However, during the synthesis of [Ru(dmbrbpy)(dmcbpy)2]2+, it was found that dmbrbpy had poor thermal stability which would cause it to form [Ru(dmcbpy)2(dmOHbpy)]2+ which would prevent the subsequent naphthopyran from reacting. Finally, Method 3 introduced AgNO₃ to remove Cl⁻ from Ru(dmcbpy)₂Cl₂, lowering the coordination temperature and allowing L62 and L64 to coordinate. After hydrolysis of CYC-62 ester and CYC-64 ester to get the target products CYC-62 and CYC-64. ¹H-NMR spectroscopy showed that after coordinating the Spiropyran unit of L62 to ruthenium, it would have both an open and closed ring structure (C/O = 1/0.6) in the DMSO-d6 solvent and would almost transform into an open ring structure (C/O: (0.08/1)), while the naphthopyran unit of L64, unlike spiropyran, remains in the closed-ring form after coordination.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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