High Molar Extinction Coefficient HeterolepticRu(II)-Mixed Ligand Polypyridyl Complexes Containing Anthracenyl and 2-Methyl-2butenoic Acid Functionalities: New
Emerging Dyes for Dye-Sensitized Solar CellApplication
Name: Dr. Adewale O. Adeloye Department of Chemistry, College of Science, Engineering and Technology, University of South Africa, Pretoria, Republic of South Africa Dye-sensitized solar cells (DSSCs; Grtzel cells) are considered one of the promising solar cell technologies of the future. Traditionally, DSSCs utilize a mesoporousnanocrystalline TiO2 film covered with ruthenium-bipyridyl-based dyes as the photoelectrode material and triiodide/iodide as the redox relay in the electrolyte. Such cells have reached conversion efficiencies above 11% at AM 1.5 solar irradiance. In the cells, the dye is one of the key components for high power conversion efficiencies. The pioneering studies using cis-dithiocyanatobis(4,4'-dicarboxylic acid-2,2'-bipyridine)ruthenium(II) (N3) is a paradigm in this field. Major drawbacks of the N3 dye are low molar extinction coefficient, durability and lack of absorption in the red region of the visible spectrum. New focus and development in the dye-sensitized solar cell research comes from the preparation of amphiphilicheteroleptic N3-equivalents, nanocrystalline TiO2 semiconductor, and/or electrolyte. It is on the basis of these major tasks of optimizing the conversion efficiencies of the DSSC that the current research work is undertaken. This work describes the synthesis and characterization of new heterolepticruthenium(II) bipyridine/phenanthroline mixed ligand complexes bearing a simple anthracene anchored on unsaturated ,-carboxylic acid functionality. The ruthenium complexes are constructed in a first step with the ligands bearing the required bromine functions, followed by a stepwise grafting of anthracene halide derivative promoted by palladiumcarbide catalysis.The UV-Vis absorption spectra of complexes in chloroform-methanol (1:1, v/v) solution displayed broad and low energy metal-to-ligand-charge transfer transitions (1MLCT) atmax between 520-700 nm ( = 3.806.60 x 103 M-1 cm-1) with a significantly enhanced band tail, improving red light absorptivity beyond 915 nm. At room temperature, complexes showed high intensity and appreciable emission wavelengths between 660 and 690 nm. The electrochemical redox properties of the complexes showed single- to multi- electronic transfer reactions. The solar to electrical energy conversion efficiency, DFT and EIS properties of the complexes are currently under investigation. Keywords:DSSCs, Ru(II) complexes, Anthracene, Polypyridine, Molar Extinction Coefficient, Luminescence, Electrochemistry Biography AdeloyeAdewaleOlufunsho received a B.Sc. (Hons.) degree Chemistry, from the Ondo State University, Ado-Ekiti, Nigeria, 1994. He proceeded to study Pharmaceutical Chemistry at the Faculty of Pharmacy, ObafemiAwolowo University, Ile-Ife, Nigeria, where he bagged a Master of Science (Pharmaceutical Chemistry) degree in 2001. While
working as an Organic Chemistry lecturer at the ObafemiAwolowo University, Ile-Ife (2003-2012), he successfully completed a Master of Philosophy degree in Chemistry (2008) with specialization in the natural products isolation and characterization. Due to the incessant electricity power challenge faced in Nigeria, he developed interest in the renewable energy (Solar Cells) research, most especially in the dye-sensitized solar cells (DSSCs). He registered for a doctoral study at the University of Fort Hare, Alice, South Africa in 2008. He completed his research work and was awarded a PhD Degree in Chemistry in 2011. His thesis entitled: Functionalized Ru(II) Polypyridines and Phthalocyanines: Potential Dyes for Dye-Sensitized Solar Cells (DSSCs) was adjudged outstanding by all external examiners. In his contribution, he successfully designed newer reaction methodology for the synthesis of certain mono-, di-, and oligo- anthracenyl functionalized polypyridine ligands and through his work, he was able to provide a rationale for the very first time that elongation of pi-bonds in organic molecules does not always result in higher molar extinction coefficient and/or shifting of wavelength maxima to the red region of the spectrum. He has 17 published articles in peer-reviewed accredited journals to his credit with an appreciable number of citation volumes. He has worked as a postdoctoral research fellow at two different universities in South Africa.
