A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes such as thiadiazole-[7]helicene and bis(thiadiazole)-[8]helicene, to boost the oxygen evolution reaction (OER) by up to ca. 130 % (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D Ni- and NiFe-based catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given.

Introduction of chirality into conducting systems is a topic of much current interest as it allows the preparation of multifunctional materials in which the chirality may modulate the structural disorder or expresses its influence through the electrical magneto-chiral anisotropy effect. The access to various chiral electroactive precursors for molecular conductors is therefore of paramount importance. Different families of chiral tetrathiafulvalene (TTF) derivatives are reviewed together with the corresponding synthetic strategies. Systems based on stereogenic carbon or sulfur atoms, axial and supramolecular chirality have been developed. In other systems the use of achiral TTFs with chiral anions has provided molecular conductors, although in most of them to date the anion is present in racemic form. Starting from some of these precursors several chiral conductors have been prepared and in two cases, involving either chiral TTF-oxazoline salts or BEDT-TTF salts with metal-oxalate anions and chiral solvent molecules, differences between the conductivity of the racemic and enantiopure forms have been found, as a consequence of the structural disorder in the solid state. Further developments in this field are expected to be directed especially towards helical architectures, possibly based on supramolecular chirality, and systems combining conductivity, magnetism and chirality in both organic and inorganic lattices.

Chiral metal dithiolene complexes represent a family of chiral precursors, which can give rise to molecular materials with properties resulting from the interplay of chirality with conductivity, magnetism, and photophysics. We describe herein the first examples of chiral metal diimine dithiolene complexes, by the use of a platinum(II) centre coordinated by 2,2′-bipyridine and helicene–dithiolene ligands. The straightforward synthesis of racemic and enantiopure complexes allows the preparation of luminescent Pt(bipy) [4] and [6]helicene compounds for which the solid-state structure was determined as well. TD-DFT calculations support the assignment of the low-energy bands observed in the UV-vis absorption spectra as mixed metal-ligand-to-ligand charge transfer transitions and confirm that the emission band results from the T₁ excited state. Interestingly, the enantiopure [6]helicene complexes show CPL activity at room temperature in acetonitrile solutions with an anisotropy factor of 3 × 10⁻⁴.