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Abstract:
Two novel alkynyl-bridged symmetric bis-tridentate ligands 1,2-bis(1′-[4′-(2,2′:6′,2″-terpyridinyl)] ferrocenyl)ethyne (3a; tpy-Fc-CC-Fc-tpy; Fc = ferrocenyl; tpy = terpyridyl) and 1,4-bis(1′-[4′-(2,2′:6′,2″-terpyridinyl)] ferrocenyl)-1,3-butadiyne (3b; tpy-Fc-CC-CC-Fc-tpy) and their Ru2+ complexes 6a and 6b have been synthesized and characterized by cyclic voltammetry, UV-vis and luminescence spectroscopy, and in the case of 3b by single-crystal X-ray diffraction. Cyclic voltammograms of both compounds, 3a and 3b, display two severely overlapping ferrocene-based oxidative peaks with only one reductive peak. The redox behavior of 6a and 6b is dominated by the Ru 2+/Ru3+ redox couple (E1/2 from 1.33 to 1.34 V), the Fe2+/Fe3+ redox couples (E1/2 from 0.46 to 0.80 V), and the tpy/tpy-/tpy2- redox couples (E 1/2 from -1.19 to -1.48 V). The UV-vis spectra of 6a and 6b show absorption bands assigned to the 1[(d(π)Fe) 6] → 1[(d(π)Fe)5(π* tpyRu)1] MMLCT transition at ∼555 nm. Complexes 6a and 6b are luminescent in H2O-CH3CN (4:1, v/v) solution at room temperature, and 6b exhibits the strongest luminescence intensity (λmaxem: 710 nm, Φem: 2.28 × 10-4, τ: 358 ns) relative to analogous ferrocene-based bis(terpyridine) Ru(ii) complexes reported so far. © 2012 The Royal Society of Chemistry.
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Dalton Transactions
ISSN: 1477-9226
Year: 2012
Issue: 36
Volume: 41
Page: 11000-11008
3 . 8 0 6
JCR@2012
3 . 5 0 0
JCR@2023
JCR Journal Grade:1
CAS Journal Grade:2
Cited Count:
SCOPUS Cited Count: 22
ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 2
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