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Issue 17, 2017
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The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties

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Abstract

The versatile rhenium complex [ReCl(CO)3(bpyC[triple bond, length as m-dash]CH)] (HC[triple bond, length as m-dash]Cbpy = 5-ethynyl-2,2′-bipyridine) is used to generate a series of bimetallic complexes through the hydrometallation of [MHCl(CO)(BTD)(PPh3)2] (M = Ru, Os; BTD = 2,1,3-benzothiadiazole). The ruthenium complex [Ru{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}Cl(BTD)(CO)(PPh3)2] was characterised structurally. Ligand exchange reactions with bifunctional linkers bearing oxygen and sulfur donors provide access to tetra- and pentametallic complexes such as [{M{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}(CO)(PPh3)2}2(S2CNC4H8NCS2)] and Fe[C5H4CO2M{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}(CO)(PPh3)2]2. The effect of the group 8 metal on the photophysical properties of the rhenium centre was investigated using the complexes [Ru{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}Cl(BTD)(CO)(PPh3)2] and [M{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}{S2P(OEt)2}(CO)(PPh3)2] (M = Ru, Os). This revealed the quenching of the rhenium-based emission in favour of weak radiative processes based on the Ru and Os centres. The potential for exploiting this effect is illustrated by the reaction of [Ru{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}Cl(CO)(BTD)(PPh3)2] with carbon monoxide, which results in a 5-fold fluorescence enhancement in the dicarbonyl product, [Ru{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}Cl(CO)2(PPh3)2], as the quenching effect is disrupted.

Graphical abstract: The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties

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Publication details

The article was received on 01 Oct 2016, accepted on 10 Nov 2016 and first published on 14 Nov 2016


Article type: Paper
DOI: 10.1039/C6DT03810G
Citation: Dalton Trans., 2017,46, 5558-5570
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    The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties

    A. Toscani, K. A. Jantan, J. B. Hena, J. A. Robson, E. J. Parmenter, V. Fiorini, A. J. P. White, S. Stagni and J. D. E. T. Wilton-Ely, Dalton Trans., 2017, 46, 5558
    DOI: 10.1039/C6DT03810G

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