Inverse Design and Synthesis of acac-Coumarin Anchors for Robust TiO2 Sensitization

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• 作者：Dequan Xiao ; Lauren A. Martini ; Robert C. Snoeberger ; III ; Robert H. Crabtree ; Victor S. Batista
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：June 15, 2011
• 年：2011
• 卷：133
• 期：23
• 页码：9014-9022
• 全文大小：1079K
• 年卷期：v.133,no.23(June 15, 2011)
• ISSN：1520-5126

文摘

An inverse design methodology suitable to assist the synthesis and optimization of molecular sensitizers for dye-sensitized solar cells is introduced. The method searches for molecular adsorbates with suitable photoabsorption properties through continuous optimization of 鈥渁lchemical鈥?structures in the vicinity of a reference molecular framework. The approach is illustrated as applied to the design and optimization of linker chromophores for TiO₂ sensitization, using the recently developed phenyl-acetylacetonate (i.e., phenyl-acac) anchor [McNamara et al. J. Am. Chem. Soc.2008, 130, 14329鈥?4338] as a reference framework. A novel anchor (3-acac-pyran-2-one) is found to be a local optimum, with improved sensitization properties when compared to phenyl-acac. Its molecular structure is related to known coumarin dyes that could be used as lead chromophore anchors for practical applications in dye-sensitized solar cells. Synthesis and spectroscopic characterization confirms that the linker provides robust attachment to TiO₂, even in aqueous conditions, yielding improved sensitization to solar light and ultrafast interfacial electron injection. The findings are particularly relevant to the design of sensitizers for dye-sensitized solar cells because of the wide variety of structures that are possible but they should be equally useful for other applications such as ligand design for homogeneous catalysis.