The complex [(tpy)Ru(tpp)RhCl(3)](PF(6))(2) (tpy = 2,2',6',2"-terpyridine and tpp = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) has been prepared and its spectroscopic, electrochemical, and photophysical properties investigated. This complex couples a ruthenium light absorber to a rhodium electron acceptor to create the first tpp-bridged light-absorber-electron-acceptor dyad. This study illustrates the applicability of this (tpy)Ru(II)(&mgr;-tpp) chromophore in the construction of photochemical molecular devices. This system is of interest since the tpp ligand has been shown to provide stereochemically defined polymetallic complexes with reasonably long-lived metal to ligand charge transfer excited states. The complex [(tpy)Ru(tpp)RhCl(3)](PF(6))(2) displays a Ru-->tpp CT transition centered at 516 nm that is the lowest lying electronic transition. The electrochemistry of [(tpy)Ru(tpp)RhCl(3)](PF(6))(2) shows a Ru(II/III) couple at 1.60 V vs Ag/AgCl, an irreversible Rh(III/I) reduction at -0.23 V and, a tpp(0/)(-) couple at -0.60 V. This illustrates that although this complex has a lowest lying spin-allowed spectroscopic transition that is Ru-->tpp CT in nature, the lowest occupied molecular orbital is Rh based. Thus, following excitation of this [(tpy)Ru(tpp)RhCl(3)](PF(6))(2) complex into the Ru-->tpp CT state, electron transfer to the rhodium is thermodyamically favorable. This electron transfer leads to a quenching of the emission normally observed for this Ru-->tpp CT excited state. Emission quenching for [(tpy)Ru(tpp)RhCl(3)](PF(6))(2) via electron transfer is 80% efficient with a k(et) of 4 x 10(7) s(-)(1). Details of these studies are presented herein.
Synthesis is unique to chemistry. Chemists make compounds, separate them from their reaction mixtures, and then determine their purity. These synthetic procedures had their origins in alchemy and, in their incarnation in modern industry, they have resulted in drugs and materials that have increased our lifetimes and have made our lives more enjoyable. Appropriate synthetic projects for the introductory laboratory should demonstrate some of the characteristics of the synthetic process:1. the same compound can be made by a number of different synthetic methods, 2. that the separation of the compound depends upon the method of preparation, and 3. that some methods of analysis are more appropriate than others for some compounds.
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