Ruthenium-Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru-Ag Coordination Polymer and Its Enhanced...

This article deals with the development of the unprecedented redox-mediated heterometallic coordination polymer {[Ru^III(acac)₂(μ-bis-η¹-N,η¹-N-BTD)₂Ag^I(ClO₄)]ClO₄} (3) via the oxidation of the monomeric building block cis-[Ru^II(acac)₂(η¹-N-BTD)₂] (1) by AgClO₄ (BTD = exodentate 2,1,3-benzothiadiazole, acac = acetylacetonate). Monomeric cis-[Ru^II(acac)₂(η¹-N-BTD)₂] (1) and [Ru^II(acac)₂(η¹-N-BTD)(CH₃CN)] (2) were simultaneously obtained from the electron-deficient BTD heterocycle and the electron-rich metal precursor Ru^II(acac)₂(CH₃CN)₂ in refluxing CH₃CN. Molecular identities of 1-3 were authenticated by their single-crystal X-ray structures as well as by solution spectral features. These results also reflected the elusive trigonal-planar geometry of the Ag ion in Ru-Ag-derived polymeric 3. Ru(III) (S = 1/2)-derived 3 displayed metal-based anisotropic EPR with ⟨g⟩/Δg = 2.12/0.56 and paramagnetically shifted ¹H NMR. Spectroelectrochemistry in combination with DFT/TD-DFT calculations of 1 and 2 (n = 1+, 0, 1-) determined a metal-based (Ru^II/Ru^III) oxidation and BTD-based reduction (BTD/BTD^•-). The drastic decrease in the emission intensity and quantum yield but insignificant change in the lifetime of 3 with respect to 1 could be addressed in terms of static quenching and/or a paramagnetism-induced phenomenon. A homogeneously dispersed dumbbell-shaped morphology and the particle diameter of 3 were established by microscopic (TEM-EDX/SEM) and DLS analysis, respectively. Moreover, the dynamic nature of polymeric 3 was highlighted by its degradation to the η¹-N-BTD coordinated monomeric fragment 1, which could also be followed spectrophotometrically in polar protic EtOH. Interestingly, both monomeric 1 and polymeric 3 exhibited efficient electrocatalytic activity toward water oxidation processes (OER, HER) on immobilization on an FTO support, which also divulged the better intrinsic water oxidation activity of 3 in comparison to 1.