The versatile rhenium complex [ReCl(CO)3(bpyCuCH)] (HCuCbpy = 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{CHvCH-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{CHvCHbpyReCl( CO)3}(CO)(PPh3)2}2(S2CNC4H8NCS2)] and Fe[C5H4CO2M{CHvCH-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{CHvCH-bpyReCl(CO)3}Cl(BTD)(CO)(PPh3)2] and [M{CHvCH-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{CHvCH-bpyReCl(CO)3}Cl(CO)(BTD)(PPh3)2] with carbon monoxide, which results in a 5-fold fluorescence enhancement in the dicarbonyl product, [Ru{CHvCH-bpyReCl (CO)3}Cl(CO)2(PPh3)2], as the quenching effect is disrupted.
The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties / Toscani, Anita; Jantan, Khairil A.; Hena, Jubeda B.; Robson, Jonathan A.; Parmenter, Emily J.; Fiorini, Valentina; White, Andrew J. P.; Stagni, Stefano; Wilton-Ely, James D. E. T.. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - STAMPA. - 46:17(2017), pp. 5558-5570. [10.1039/c6dt03810g]
The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties
FIORINI, VALENTINA;STAGNI, STEFANO;
2017
Abstract
The versatile rhenium complex [ReCl(CO)3(bpyCuCH)] (HCuCbpy = 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{CHvCH-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{CHvCHbpyReCl( CO)3}(CO)(PPh3)2}2(S2CNC4H8NCS2)] and Fe[C5H4CO2M{CHvCH-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{CHvCH-bpyReCl(CO)3}Cl(BTD)(CO)(PPh3)2] and [M{CHvCH-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{CHvCH-bpyReCl(CO)3}Cl(CO)(BTD)(PPh3)2] with carbon monoxide, which results in a 5-fold fluorescence enhancement in the dicarbonyl product, [Ru{CHvCH-bpyReCl (CO)3}Cl(CO)2(PPh3)2], as the quenching effect is disrupted.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.