蔡明剛Ming-Kang Tsai黃鈺庭Yu-Ting Huang2019-09-042017-6-262019-09-042012http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0699420699%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100966Ruthenium結合non-innocent ligands(NILs)錯合物具有非常有趣的electronic properties，已知在benzoquinone、iminobenzoquinone、benzoquinonediimine等系統中以及它們相對應的redox衍生物中均可觀察到這些現象。本篇研究針對[Ru(dcbpy)2(8-OQN)]+ (dcbpy=4, 4'- dicarboxy-2, 2' bipyridyl, and 8-OQN=8-oxyquinolate)這個錯合物進行電子結構的分析，以及其在太陽能染料電池上的應用。本篇論文藉由結合分子軌道理論與密度泛函理論的方式來研究[Ru(dcbpy)2(8-OQN)]+的特性。在考量溶劑效應下，我們計算[Ru(dcbpy)2(8- OQN)]+幾何結構、電子結構和吸收圖譜來探討。我們的結果顯示在吸收圖譜上有強的Ru (dπ) → dcbpy (π*) MLCT的吸收在300-700 nm的範圍內，以及在電子結構中，Ru d(π) 和 8-QON p(π)的軌域是混成在一起的。從研究結果發現，[Ru(dcbpy)2 (8-OQN)]+顯示出和[Ru(dcbpy)2(dfpp)]+ (dfpp=2-(2, 4-Difluororphenyl)pyridine) 及 Ru(dcbpy)2(NCS)2相近氧化還原電位、電子結構和吸收圖譜。我們也加入[Ru(dcbpy)2(5,7-di-X-8-OQN)]+ (X=F, Cl, Br, I, Me)和[Ru(dcbpy)2 (2,4-di-Y-phenyl-pyridine)]+ (Y= F, Cl, Br, I, Me)系列的錯合物做計算，觀察加入推拉電子基對吸收光譜、電子結構和分子軌域的影響。最後藉由[Ru(dcbpy)2(5,7-di-X-8-OQN)]+和[Ru(dcbpy)2 (2,4-di-Y-phenyl-pyridine)]+與電解質模型I-的計算，從軌道能量的觀點上，發現I-無法對[Ru(dcbpy)2(5,7-di-X-8-OQN)]+系列錯合物的HOMO進行還原。Ruthenium complexes with non-innocent ligand, e.g. benzoquinone、iminobenzoquinone、benzoquinonediimine, exhibit intriguing electronic properties. [Ru(dcbpy)2(8-OQN)]+ (dcbpy = 4, 4'- dicarboxy-2, 2' bipyridyl, and 8-OQN = 8-oxyquinolate) for dye-sensitized solar cells was designed and reported. We report herein a theoretical investigation combinging molecular orbital theory and Density Functional Theory (DFT) on the [Ru(dcbpy)2 (8-OQN)]+. Molecular geometries, electron structures, and optical absorption spectra are predicted in methanol solution. Our results show that [Ru(dcbpy)2(8-OQN)]+ displays Ru (dπ) → dcbpy (π*) metal-to-ligand charge transfer absorption spectra in the range of 300-700 nm and extended molecular orbital overlap due to Ru (dπ) and 8-QON p(π) mixing. [Ru(dcbpy)2(8-OQN)]+ show similar redox potentials, optical properties and electron structures in comparison with [Ru(dcbpy)2(dfpp)]+ (dfpp=2-(2,4-Difluororphenyl) pyridine) and Ru (dcbpy)2(NCS)2complexes using the optimized structures. Furthermore, a series of [Ru(dcbpy)2(5,7-di-X-8-OQN)]+ (X=F, Cl, Br, Me) Ru-8-OQN_F, Ru-8-OQN_Cl, Ru-8-OQN_Br and Ru-8-OQN_Me and [Ru(dcbpy)2 (2,4-di-Y-phenyl-pyridine)]+ (Y=H, Cl, Br, Me) YE05_H, YE05_Cl, YE05_Br and YE05_Me have been characterized by absorption spectra, electron structures and molecular orbitals. A quantative model of describing electrolyte (I¯ ion) was carried out using molecular orbital theory. The enegetics of the p orbitals of I¯ ions suggests that the electron injection into HOMO of [Ru(dcbpy)2(5,7-di-X- 8-OQN)]+ complexes may not be possible.太陽能染料電池Dye-Sensitized Solar Cellsnon-innocent