<p> </p>
<p>This thesis will focus on two broad topics: the synthesis and characterization of various diruthenium aryl compounds and of mono- and bis-alkynyl unsymmetric compounds based on Ru(II)(dppm)<sub>2</sub> and Ru(II)(dppe)<sub>2</sub> bridges (dppm = 1,2-bis(diphenylphosphino)methane; dppe = 1,2-bis(diphenylphophino)ethane).</p>
<p>Chapters 1–3 focus on multiply bonded metal–metal compounds, utilizing four different ‘paddlewheel’ motifs (dinuclear ruthenium units that are supported by four bidentate ligands). These highly stable mono- and bis-aryl diruthenium compounds are readily prepared using lithium-halogen exchange reactions. Two different oxidation states have been accessed, Ru<sub>2</sub>(II,III) and Ru<sub>2</sub>(III,III), through modification of the paddlewheel ligands or coordination of a small, π-accepting ligand at the vacant ruthenium site in Ru<sub>2</sub>(<em>ap</em>)<sub>4</sub>(Ar) compounds (<em>ap</em> = 2-anilinopyridinate; Ar = aryl). Chapter 1 discusses the modification of the bidentate ligand to yield two unique Ru<sub>2</sub>(<em>ap</em>')<sub>4</sub>(Ar) series, which both exhibit improved solubility over the previously reported un-modified Ru<sub>2</sub>(<em>ap</em>)<sub>4</sub>(Ar) series, and the structural, electronic, and optical characterizations of the compounds within these two new Ru<sub>2</sub>(II,III) series. Chapter 2 builds upon our lab’s previous studies on electron transfer between the two ruthenium centers in [Ru<sub>2</sub>(<em>ap</em>)<sub>4</sub>]<sub>2</sub>(μ-C≡C)<sub>x</sub> compounds and applies this towards synthesizing and characterizing mixed-valency within a Ru<sub>2</sub>(III,III) phenylene bridged compound [(NC)Ru<sub>2</sub>(<em>ap</em>)<sub>4</sub>]<sub>2</sub>(μ-1,4-C<sub>6</sub>H<sub>4</sub>). Chapter 3 highlights the synthesis and characterization of bis-aryl and bis-alkynyl Ru2(III,III) compounds, Ru<sub>2</sub>(amtfmp)<sub>4</sub>(Y)<sub>2</sub> (Y = -C≡CPh, -Ph), supported with the electron-withdrawing paddlewheel ligand amtfmp (amtfmp = 2-amino-3-(trifluoromethyl)pyridinate). </p>
<p>Chapters 4 and 5 are focused on the synthesis and characterization of both mono- and bis-alkynyl unsymmetric compounds to study photo-induced electron transfer (PET) processes. Chapter 4 features as an introduction to the synthesis of these Ru(II)(dppm)<sub>2</sub> and Ru(II)(dppe)<sub>2 </sub>alkynyl compounds along with some material applications. Chapter 5 discusses the mono- and bis-alkynyl compounds based on Ru(II)(dppm)<sub>2</sub> and Ru(II)(dppe)<sub>2</sub> bridges that utilized a highly electron-withdrawing chromophore ‘acceptor’ ligand, NAP<sup>R</sup> (R = isopropyl, mesityl), to generate the <em>B-A</em> (mono-alkynyl) and <em>D-B-A</em> (unsymmetric bis-alkynyl) compounds.</p>
| Identifer | oai:union.ndltd.org:purdue.edu/oai:figshare.com:article/21603387 |
| Date | 23 November 2022 |
| Creators | Lyndsy Ann Miller-Clark (14158776) |
| Source Sets | Purdue University |
| Detected Language | English |
| Type | Text, Thesis |
| Rights | CC BY 4.0 |
| Relation | https://figshare.com/articles/thesis/Dissertation_LyndsyMC_pdf/21603387 |
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