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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)(PPh 3 ) 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)(PPh 3 ) 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)(PPh 3 ) 2 } 2 (S 2 CNC 4 H 8 NCS 2 )] and Fe[C 5 H 4 CO 2 M{CH[double bond, length as m-dash]CH-bpyReCl(CO) 3 }(CO)(PPh 3 ) 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)(PPh 3 ) 2 ] and [M{CH[double bond, length as m-dash]CH-bpyReCl(CO) 3 }{S 2 P(OEt) 2 }(CO)(PPh 3 ) 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)(PPh 3 ) 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 (PPh 3 ) 2 ], as the quenching effect is disrupted.