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Walsh JJ, Zhu J, Zeng Q, et al. Self assembled composites of luminescent Ru(II) metallopolymers and the Dawson polyoxometalate α-[Mo18O54(SO4)2]4-. Dalton Trans. 2012;41(33):9928-37doi: 10.1039/c2dt30503h.
Walsh, J. J., Zhu, J., Zeng, Q., Forster, R. J., & Keyes, T. E. (2012). Self assembled composites of luminescent Ru(II) metallopolymers and the Dawson polyoxometalate α-[Mo18O54(SO4)2]4-. Dalton transactions (Cambridge, England : 2003), 41(33), 9928-37. https://doi.org/10.1039/c2dt30503h
Walsh, James J, et al. "Self assembled composites of luminescent Ru(II) metallopolymers and the Dawson polyoxometalate α-[Mo18O54(SO4)2]4-." Dalton transactions (Cambridge, England : 2003) vol. 41,33 (2012): 9928-37. doi: https://doi.org/10.1039/c2dt30503h
Walsh JJ, Zhu J, Zeng Q, Forster RJ, Keyes TE. Self assembled composites of luminescent Ru(II) metallopolymers and the Dawson polyoxometalate α-[Mo18O54(SO4)2]4-. Dalton Trans. 2012 Sep 07;41(33):9928-37. doi: 10.1039/c2dt30503h. Epub 2012 Jun 06. PMID: 22674209.
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Dalton Trans. 2012 Sep 07;41(33):9928-37. doi: 10.1039/c2dt30503h. Epub 2012 Jun 06.

Self assembled composites of luminescent Ru(II) metallopolymers and the Dawson polyoxometalate α-[Mo18O54(SO4)2]4-.

Dalton transactions (Cambridge, England : 2003)

James J Walsh, Jie Zhu, Qiang Zeng, Robert J Forster, Tia E Keyes

Affiliations

  1. School of Chemical Sciences, National Centre for Sensor Research, Dublin City University, Glasnevin, Dublin 9, Ireland.

PMID: 22674209 DOI: 10.1039/c2dt30503h

Abstract

The interaction of two luminescent metallopolymers; [Ru(bpy)(2)(PVP)(10)](2+) and [Ru(bpy)(2)(CAIP)co-poly(7)](+), where bpy is 2,2'-bipyridyl, PVP is polyvinylpyridine, and (CAIP)co-poly(7) is poly(styrene(6)-co-p-(aminomethyl)styrene) amide linked to 2-(4-carboxyphenyl)imidazo[4,5-f] [1,10]phenanthroline, with the Dawson polyoxomolybdate α-[Mo(18)O(54)(SO(4))(2)](4-) is described. Both metallopolymers undergo electrostatic association with the polyoxometalate. From both electronic and luminescence spectroscopy the thermodynamic products were determined to be {[Ru(bpy)(2)(PVP)(10)](4.5)[Mo(18)O(54)(SO(4))(2)]}(5+) and {[Ru(bpy)(2)(CAIP)co-poly(7)](5)[Mo(18)O(54)(SO(4))(2)]}(+), i.e. in both instances, the number of ruthenium centres in the cluster exceeds the number required for charge neutralization of the molybdate centre. Association quenches the luminescence of the metallopolymer although, consistent with the excess of Ru(ii) present in the associated composites, emission is not completely extinguished even when a large excess of [Mo(18)O(54)(SO(4))(2)](4-) is present. The observed emission lifetime was not affected by [Mo(18)O(54)(SO(4))(2)](4-) therefore quenching was deemed static. The luminescent intensity data was found to fit best to a (sphere of action) Perrin model from which the radii of the quenching were calculated as 4.6 Å and 5.8 Å for [Ru(bpy)(2)(PVP)(10)](2+) and [Ru(bpy)(2)(CAIP co-poly)(7)](+) respectively. Both UV/Vis and resonance Raman data indicate the presence of a new optical transition centered around 490 nm for the composite, {[Ru(bpy)(2)(PVP)(10)](4.5)[Mo(18)O(54)(SO(4))(2)]}(5+) but not for {[Ru(bpy)(2)(CAIP)co-poly(7)](5)[Mo(18)O(54)(SO(4))(2)]}(+). This indicates strong electronic interaction between the metal centres in the former composite, which despite good thermodynamic analogy, is not observed for {[Ru(bpy)(2)(CAIP)co-poly(7)](5)[Mo(18)O(54)(SO(4))(2)]}(+). These results are consistent with photoelectrochemical studies of layer by layer assemblies of these films which indicate that the ruthenium centre sensitizes polyoxometalate photo-oxidation of benzyl alcohol in {[Ru(bpy)(2)(PVP)(10)](4.5)[Mo(18)O(54)(SO(4))(2)]}(5+) but not in {[Ru(bpy)(2)(CAIP)co-poly(7)](5)[Mo(18)O(54)(SO(4))(2)]}(+).

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