Green Chemistry Strategies for Organic Synthesis and Solar Energy Applications

The need for safer chemical practices and conservation of raw materials is a growing necessity in a rapidly evolving world. Green chemistry, the development of environmentally sustainable chemical processes, was pioneered by current Yale University professor Paul Anastas and his then-colleague John Warner in 1998. The "12 Principles of Green Chemistry," outlined in Green Chemistry: Theory and Practice, include suggestions for small- and large-scale applications, many of which have been widely adopted over the past decade.;The following chapters presented in this dissertation focus on some of these principles and how they are relevant to all of the work described here. Specifically, Chapter 2 presents a 3-step, one-pot C-C bond forming reaction that is not only atom economical, but also reduces hazardous waste. Benzylic secondary alcohols can be alkylated in good yields at the beta-position with primary alcohols. The reaction is promoted by KOH and NaOH, eliminating the need for transition metal catalysts.;In Chapters 3-5, the syntheses of terpyridine-based anchor-linker scaffolds for solar energy applications are presented. The diverse functional groups available in terpyridines provide synthetic handles that will be utilized in subsequent syntheses. Synthesis of robust, polypyridyl-based ligands containing acetylacetone (acac) anchors for attachment to nanoparticle surfaces and their possible molecular rectification effects are presented. Convergent syntheses of novel building blocks provide routes to several ligand analogues bearing similar functional groups but differing in connectivity. Computational studies have suggested this connectivity difference could lead to interesting molecular rectification effects, and this phenomenon is being investigated through electron paramagnetic resonance (EPA) spectroscopy as well as scanning tunneling microscopy (STM). Special care was taken in these syntheses to develop efficient methodologies that not only increase the yield of the desired product, but also eliminate unnecessary purification and derivitization sequences when possible.;Efficiency in solar-driven processes, such as photoelectrochemical cells and dye-sensitized solar cells (DSSCs), relies on strong electronic coupling between a semiconductor and a surface-bound light absorber. Recent developments by Coppens and co-workers at SUNY Buffalo have enabled the study of solar-relevant anchor groups on well-defined polyoxotitanates (POTs) that mimic single-crystal and nanoparticulate titanium dioxide (TiO2). The syntheses and X-ray diffraction studies of acac anchors incorporated into simple arenes and more complex terpyridine and phenanthroline ligands are presented. Attachment of these molecules to POTs and subsequent X-ray diffraction have provided insight into acac binding modes on TiO2.