Example 1. The motivation for the work presented here is to put the phenomenon of synergistic reactivity of two redox active metal sites on a mechanistic basis. With regard to the importance of structures in Nature that comprise multiple metals, understanding the mechanistic details of cooperative behaviour of an ensemble of redox active metal atoms is relevant to the search for strategies toward the efficient interconversion of electrical and chemical bond energies.

Novel bimetallic complexes of nickel of a dithiophenol scaffold mediate both formation and oxidation of dihydrogen, just depending on the oxidation state of the bimetallic metal-sulphur core. Essential properties of the ligand include its capability to couple the metals electronically in different formal redox-states and shuttle protons to and from the reactive bimetallic core.

Example 2. Sulphur-bridged di- and multinuclear structures play a pivotal role in a variety of processes that are essential to life. We aim at understanding the effect of the electronic properties of the sulphur linkage on the properties of metal-sulphur cores. How do 2M-2S structures assemble and how does this relate to function? We studied redox-induced skeletal (dis)assembly of a [Ni₂(µ-thiolate)₂] core quantitatively as shown in case A) below. And what factors contribute to modulating electronic coupling in 2M-2S structures? Charged coligands do! We probed their impact by (pulse)EPR spectroscopy and comprehensive DFT modelling as shown in case B) below. According to our model, 2M-2S sites perform like a molecular transistor: Charge flows from source to drain as long as intracore coupling does not prevail, which is achieved due to charge donation from peripheral donors (equal to applying a base voltage). Otherwise, charge flow through the 2M-2S site would be blocked. Our model platform provided detailed insights regarding the properties of natural Cu_A and 2Fe-ferredoxins, and contributes to advancing the general understanding of one of nature’s functionally multifaceted structures.
 

Example 3. Metal complexes of radical ligands feature exciting physical and chemical properties that relate to their intriguing electronic structures. Each of the four complex cations of a group 10 metal drawn below features an open-shell thiolate ligand, which is why these compounds exhibit intense low-energy electronic transitions. The radical-ligand cations of platinum feature divergent chromophore properties although chemical compositions are very similar or even identical. Inter- and intraligand steric interactions result in subtle differences between molecular structures, rendering the three [(S^-)Pt(^●S)]⁺ chromophores electronically distinct.