紫質供受體衍生物之合成及其基本性質研究

在本論文中，以乙炔苯基（ethynylphenyl）為架橋分子，利用了Sonogashira cross-coupling reaction方法，合成出了紫質供受體化合物。我們所選用的紫質（P）為10, 20-biphenylporphinato zinc(II)及10, 20-bis(3,5-di-tert-butyl-phenyl)porphinato zinc(II)，將與紫質相較為電子受體的富勒烯（fullerene；C60）與紫質相較為電子供體的二茂鐵（ferrocene；Fc）各別成功接上紫質。分析紫質供受體化合物的在光譜學、電化學及光電轉換的性質加以探討。在這些供體—橋鍵—受體（Donor-Bridge-Acceptor；D-B-A）分子化合物中，我們從紫外光—可見光吸收光譜發現，富勒烯—紫質供受體在基態的吸收能保有原本的吸收特徵峰，紫質供受體分子沒有因為橋鍵的連接，互相影響造成吸收光譜的吸收位置；二茂鐵—紫質供受體由於連接處不完全非共軛，所以紫質的特徵吸收在B band有變寬變弱，且在Q band有些為紅移。在電化學方面，供體、受體分子的氧化還原電位，也沒有因為兩者鍵結在一起而大幅改變。所以，我們從氧化還原電位了解，由於富勒烯的還原反應較紫質先發生，容易還原得到電子；二茂鐵的氧化反應較紫質先發生，容易氧化失去電子。從螢光放射光譜中可以推測出，光誘導電子轉移的機制，碳六十受體紫質，在紫質被激發後，富勒烯容易接收電子使得在激發態的紫質螢光被削弱。另外，二茂鐵供體紫質，在紫質被激發後，二茂鐵容易提供電子給激發態的紫質，使得紫質螢光被削弱。推測所有的紫質供受體分子都有電子轉移產生電荷分離。在染料敏化太陽能電池的應用上，測量紫質供受體的光電轉換效率，得到總轉換效率C60-P為0.11 %、Fc-P為0.32 %。

關鍵字

紫質；富勒烯；二茂鐵；電子轉移；敏化染料太陽能電池

並列摘要

Donor/acceptor-porphyrin dyads are successfully synthesized by cross-coupling method. The spectroscopy, redox properties and photovoltaic performance were studied. We chose 10, 20-biphenylporphinato zinc(II) and 10, 20-bis(3,5- di-tert-butyl-phenyl) porphinato zinc(II) as basic porphyrin (P) moieties to combine with fullerene ( C60) and with ferrocene (Fc). The ground-state UV-Visible spectra are a superimposition of the spectral features of the individual component, suggesting little interaction between the C60 and porphyrin moieties. For Fc-P dyads, the B band become broadened and weaker, and the Q band are red shift. This is consistent with the electrochemical data: Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) experiments, show that C60 induces first, indicatng C60 accepted electron more easily than porphyrin. On the other hand, the oxidizes first, indicating Fc as an electron donor. The steady-state fluorescence spectra indicate that the porphyrin fluorescence in the dyads is very strongly quenched at room temperature. The mechanism of photoinduced electron transfer, C60 captured electron after porphyrin was excited in C60-P and the Fc donated its electron to excited porphyrin in Fc-P. For the DSSC performance, the overall efficiencies were 0.32 % and 0.11 %.

並列關鍵字

porphyrin ； fullerene ； ferrocene ； electron transfer ； DSSC

參考文獻

1. Alivisatos, A. P.; Barbara, P. F.; Castleman, A. W.; Chang, J.;Dixon, D. A.; Klein, M. L.; McLendon, G. L.; Miller, J. S.; Ratner, M.A.; Rossky, P. J.; Stupp, S. I.; Thompson, M. E. Adv. Mater. 1998, 10, 1297-1336.

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