Bimetallic complexes have been shown to exhibit high electrocatalytic and photocatalytic activity, specifically proton reduction. Dirhodium compounds having a paddlewheel structure with a Rh-Rh bond have become promising candidates for this reaction and CO2 reduction with high turnover numbers and catalytic efficiency. Recently, dinuclear complexes with short metal-metal bond distance such as cis- [Rh2(DToLF)2(bncn)2]2+ (bncn = benzo[c]cinnoline) have been shown to possess long lived triplet excited state and work as a single molecular photocatalyst for proton reduction under red light with good turnover number. To further understand the mechanism of such compounds, the present work focuses on the studying similar complexes with uncapped axial sites and exchanging bridging ligands. Two different types of heteroleptic compounds of the form cis- [Rh2(DPhF)(OAc)(bncn)2][BF4]2 (1) and cis- [Rh2(DPhF)(OAc)(bncn)(np)][BF4]2 (2) (DPhF = N,N′-diphenylformamidinate; OAc = acetate; np = 1,8-naphthyridine) are being explored. Substituting these ligand positions alters the HUMO-LUMO transition and offer insight in the importance of two of these ligands each. The latter compound is first of its kind with a tetraheteroleptic environment around the Rh2(II,II) core. This poster aims to discuss the synthetic routes for preparation of these complexes followed by their spectroscopic, electrochemical and structural properties granting an insight into their lifetimes and mechanism for proton reduction.

Heteroleptic dirhodium(II,II) paddlewheel complexes for electro- and photocatalytic proton reduction

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