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Toward the Development of Molecular Wires: Ruthenium(II)Terpyridine Complexes Containing Polyferrocenyl as SpacerChen, Kellen 15 July 2005 (has links)
The preparations of multinuclear supramolecules assembled from 1,1¡¬-bis(terpyridyl)ferrocene, 1,1¡¬-bis(terpyridyl)biferrocene and 1,1¡¬-bis(terpyridyl)triferrocene (tpy-(fc)n-tpy, n =1-3) redox-active moieties with Ru2+ metal centers are described. The electrochemical measurements of the Ru2+ coordinated tpy-(fc)n-tpy complexes (1a (n=1); 1b (n=2); 1c (n=3)) are dominated by the Ru2+/Ru3+ redox couple (E1/2 from 1.35 to 1.38 V), Fe2+/Fe3+ redox couples (E1/2 from ∼0.4 to ∼1.0 V) and tpy/tpy-/tpy2- redox couples (E1/2 from 1.3 to 1.5 V). The appreciable variations detected in the Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the spacer and the Ru2+ metal centers. On the coordination of Ru2+ metal centers with tpy-(fc)n-tpy rises to a red-shifted and more intense 1[(d(£k)Fe)6] ¡÷ 1[d(£k)Fe)5(£k*tpyRu)1] transition in the visible region. The observed red-shifted absorption from 526 nm in monomeric [Ru(fctpy)2]2+ complex to ~560 nm in 1b and 1c reveals that there is a qualitative electronic coupling within the ferrocenyl array. The Fe-Fe interactions result in a red characteristic of the 1[(d(£k)Fe)6] ¡÷ 1[d(£k)Fe)5(£k*tpyRu)1] MMLCT transition.
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