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Issue 43, 2013
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Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine)ruthenium(II) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

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Abstract

Hydrogen sulfate salts of [Ru(1)2]2+ where 1 = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and four N-alkylated derivatives [Ru(L)2]4+ were used as photosensitizers (λmax ∼510 nm) for water oxidation in light driven reactions with peroxydisulfate as a sacrificial electron acceptor and Na10[Co4(H2O)2(α-PW9O34)2] (Co4POM) as the catalyst in sodium borate buffers at pH 8.0 and 9.0. The N-substituents investigated were benzyl (L+ = 2+), ethyl (L+ = 3+), allyl (L+ = 4+) and 4-cyanobenzyl (L+ = 5+). The O2 yield in the presence of [Ru(L)2]4+ (L+ = 2+–4+) was comparable to that obtained in the presence [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) using light sources with λmax ≈ 490 nm. The ruthenium(III) complexes [Ru(1)2]3+ and [Ru(L)2]5+ (L+ = 2+–5+) are rather unstable in acidic conditions and could not be isolated. The most efficient photosensitizers [Ru(L)2]5+ (L+ = 2+ and 4+) were the least stable under weakly basic conditions (pH 9.0) with a half-life τ1/2 ∼ 10 ms. The stability of the complexes under photocatalytic turnover conditions is probably controlled by the rate at which ligand L+ is oxidized by Co4POM in its highest oxidation state.

Graphical abstract: Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine)ruthenium(ii) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

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Publication details

The article was received on 24 Apr 2013, accepted on 19 Aug 2013 and first published on 11 Sep 2013


Article type: Paper
DOI: 10.1039/C3RA44192J
Citation: RSC Adv., 2013,3, 20647-20654
  • Open access: Creative Commons BY license
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    Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine)ruthenium(II) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

    H. Lv, J. A. Rudd, P. F. Zhuk, J. Y. Lee, E. C. Constable, C. E. Housecroft, C. L. Hill, D. G. Musaev and Y. V. Geletii, RSC Adv., 2013, 3, 20647
    DOI: 10.1039/C3RA44192J

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