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.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0715105-140426 |
| Date | 15 July 2005 |
| Creators | Chen, Kellen |
| Contributors | none, Teng-Yung Dong, none, Lan-Chang Liang |
| Publisher | NSYSU |
| Source Sets | NSYSU Electronic Thesis and Dissertation Archive |
| Language | Cholon |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0715105-140426 |
| Rights | withheld, Copyright information available at source archive |
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