The Chirality Induced Spin Selectivity (CISS) effect describes the capability of chiral molecules to act as spin filters discriminating flowing electrons according to their spin state. Within molecular spintronics, efforts are focused on developing chiral-molecule-based technologies to control the injection and coherence of spin-polarized currents. Herein, for this purpose, we study spin selectivity properties of a monolayer of a thioalkyl derivative of a thia-bridged triarylamine hetero[4]helicene chemisorbed on a gold surface. A stacked device assembled by embedding a monolayer of these molecules between ferromagnetic and diamagnetic electrodes exhibits asymmetric magnetoresistance with inversion of the signal according to the handedness of molecules, in line with the presence of the CISS effect. In addition, magnetically conductive atomic force microscopy reveals efficient electron spin filtering even at unusually low potentials. Our results demonstrate that thia[4]heterohelicenes represent key candidates for the development of chiral spintronic devices.

The chirality-induced spin selectivity (CISS) effect is the capability of chiral molecules to act as spin filters, i.e. to selectively sort flowing electrons based on their spin states. The application of this captivating phenomenon holds great promise in the realm of molecular spintronics, where the primary focus lies in advancing technologies based on chiral molecules to regulate the injection and coherence of spin-polarized currents. In this context, we conducted a study to explore the spin filtering capabilities of a monolayer of the thia-bridged triarylamine hetero[4]helicene radical cation chemisorbed on a metallic surface. Magnetic–conductive atomic force microscopy revealed efficient electron spin filtering at exceptionally low potentials. Furthermore, we constructed a spintronic device by incorporating a monolayer of these molecules in between two electrodes, obtaining an asymmetric magnetoresistance trend with signal inversion in accordance with the handedness of the enantiomer involved, indicative of the presence of the CISS effect. Our findings underscore the significance of thia[4]azahelicene organic radicals as promising candidates for the development of quantum information operations based on the CISS effect as a tool to control the molecular spin states.

In the past few years, the chirality and magnetism of molecules have received notable interest for the development of novel molecular devices. Chiral helicenes combine both these properties, and thus their nanostructuration is the first step toward developing new multifunctional devices. Here, we present a novel strategy to deposit a sub‐monolayer of enantiopure thia[4]helicene radical cations on a pre‐functionalized Au(111) substrate. This approach results in both the paramagnetic character and the chemical structure of these molecules being maintained at the nanoscale, as demonstrated by in‐house characterizations. Furthermore, synchrotron‐based X‐ray natural circular dichroism confirmed that the handedness of the thia[4]helicene is preserved on the surface.

We have developed an efficient chemical resolution of racemic hydroxy substituted dithia-aza[4]helicenes (DTA[4]H) 1(OH) using enantiopure acids as resolving agents. The better diastereomeric separation was achieved on esters prepared with (1S)-(−)-camphanic acid. Subsequent simple manipulations produced highly optically pure (≥ 99% enantiomeric excess) (P) and (M)-1(OH) in good yields. The role of the position where the chiral auxiliary is inserted (cape- vs. bay-zone) and the structure of the enantiopure acid used on successful resolution are discussed.

Dithiabridged triarylamine hetero[4]helicenes are an interesting class of chiral compounds characterized by a high racemization barrier which makes them an attractive material for several applications. Their rich redox chemistry allows one to obtain radical cations stable at room temperature, that can be isolated in two configurationally stable enantiomers. While several studies have been reported on systems with transition metals possessing low‐lying electronic states, the characterization of purely organic open‐shell systems by VCD is still scarce. This may be due to the instability of radical‐cation species and to the dark color assumed by the solution at the high concentration required by VCD. The oxidation of this molecular system shifts the first electronic transition towards the Near‐IR (NIR) region, at approximately 1250 nm. By combining ECD, VCD, MCD, NIR‐CD and computational methodologies rooted in density functional theory, we have investigated one molecule of this class of compounds and shed some light on the chiroptical properties accessible via redox‐switch.