Issue 17, 2017

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

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

Supplementary files

Article information

Article type
Paper
Submitted
01 Mph 2016
Accepted
10 Pun 2016
First published
14 Pun 2016

Dalton Trans., 2017,46, 5558-5570

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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