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Self‐assembling features, chiroptical activity, and spin filtering properties are reported for 2,15‐ and 4,13‐disubstituted [6]helicenes decorated in their periphery with 3,4,5‐tris(dodecyloxy)‐N‐(4‐ethynylphenyl)benzamide moieties. The weak non‐covalent interaction between these units conditions the corresponding circularly polarized luminescence and spin polarization. The self‐assembly is overall weak for these [6]helicene derivatives that, despite the formation of H‐bonding interactions between the amide groups present in the peripheral moieties, shows very similar chiroptical properties both in the monomeric or aggregated states. This effect could be explained by considering the steric effect that these groups could generate in the growing of the corresponding aggregate formed. Importantly, the self‐assembling features also condition chiral induced spin selectivity (CISS effect), with experimental spin polarization (SP) values found between 35–40 % for both systems, as measured by magnetic‐conducting atomic force microscopy (AFM) technique. [ABSTRACT FROM AUTHOR]

Chiral perovskites (CPs) have attracted enormous attentions since they have combined chirality and optoelectrical properties well which is promising in circularly polarized luminescence (CPL) application and of great importance for future spin-optoelectronics. However, there is a key contradiction that in chiral perovskites chirality distorts the crystal structure, leading to poor photoluminescence (PL) properties. Achieving the balance between chirality and PL is a major challenge for strong CPL from chiral perovskites. Differently, two-dimensional (2D) chiral perovskite has shown fascinating chiral induced spin selectivity (CISS) effect which can act as spin injector under ambient conditions. Here, we propose an effective strategy to achieve high CPL activity generated from quantum dots (QDs) by introducing 2D chiral perovskite as a chiral source, providing spin polarized carriers through the CISS effect. The as-synthesized QDs/CP composites exhibit dissymmetry factors (glum) up to 9.06 × 10−3. For the first time, we performed grazing incident wide angle X-ray scattering (GIWAXS) measurements, showing the chirality originates from the distorted lattices caused by the large chiral organic cations. Besides, time-resolved PL (TR-PL) measurements verify the enhanced CPL activity should be attributed to the charge transport between two components. These findings provide a useful method to achieve CPL in QDs/2D chiral perovskite heterojunctions which could be promising in spin-optoelectronics application. [ABSTRACT FROM AUTHOR]

Electrons ransported through a chiral molecule become spin−polarized; this phenomenon is known as chiral induced spin selectivity (CISS). It has implications for spintronics, for electrochemical and enantioselective reactions, and for electron transfer in biological systems. The CISS‐induced spin polarization in simulations and in experiment differs by orders of magnitude, and the detailed underlying mechanism is still an open question. Structure−property relationships can help elucidate this question. For this purpose, the effect of helix pitch is studied for a model helix of 20 carbon atoms for two quantities which have been found to correlate in some experiments: spin‐polarization in transmitted electrons and electronic circular dichroism (ECD). We find that even though the chirality of these model helices goes down with increased pitch, ECD and CISS go up, along with ultraviolet−visible (UV/Vis) spectra and magnetic and electric transition dipole moments. Orbital contributions to the most intense UV/Vis transition do not show a consistent qualitative picture. Tentatively, we can assign the increase in these properties to an increase of the electric polarizability with spatial extension of these helices by changing pitch. [ABSTRACT FROM AUTHOR]

Chirality in life has been preserved throughout evolution. It has been assumed that the main function of chirality is its contribution to structural properties. In the past two decades, however, it has been established that chiral molecules possess unique electronic properties. Electrons that pass through chiral molecules, or even charge displacements within a chiral molecule, do so in a manner that depends on the electron's spin and the molecule's enantiomeric form. This effect, referred to as chiral induced spin selectivity (CISS), has several important implications for the properties of biosystems. Among these implications, CISS facilitates long-range electron transfer, enhances bio-affinities and enantioselectivity, and enables efficient and selective multi-electron redox processes. In this article, we review the CISS effect and some of its manifestations in biological systems. We argue that chirality is preserved so persistently in biology not only because of its structural effect, but also because of its important function in spin polarizing electrons. [ABSTRACT FROM AUTHOR]

Electrochemical water splitting is considered as a promising approach to storing renewable electricity in the form of hydrogen fuel. In this work, we report the design and electrocatalytic properties of chiral CuO@Ni with three dimensional (3D) continuous macroporous framework. With the chiral CuO@Ni as anode, the OER overpotential required to achieve the current density of 10 mA/cm2 was as low as 110 mV in 0.1 M KOH electrolyte, and the hydrogen production rate of water splitting reaction could reach 1070 nL/s. Moreover, the OER overpotential could be regulated easily by controlling the deposition time of chiral CuO layer on Ni. The high catalytic activity of chiral CuO@Ni for water splitting is closely associated with the Chiral-induced spin selectivity ( CISS ) effect, the large reactive area provided by its 3D macroporous structure, and the effective cooperation between chiral CuO and Ni foam that facilitated the transportation of spin aligned electrons from chiral CuO layer to Ni. The results shown in this work indicate a simple and promising strategy to improve the electrocatalytic activity of other chiral earth-abundant catalysts for water splitting. This work shows the design and properties of chiral CuO@Ni with three dimensional continuous macroporous framework. The chiral CuO@Ni exhibited lower OER overpotential and larger current density than many CuO-based catalysts. Its high catalytic activity for water splitting reaction is attributed to the CISS effect of chiral CuO, the large reactive area of its 3D porous structure, and the synergistic interaction between the chiral CuO and the Ni foam. Image 1 • Chiral CuO@Ni with three dimensional continuous macroporous framework. • Low OER overpotential (110 mV) to achieve 10 mA/cm2 current density. • Easy and effective way to enhance the activity of chiral earth-abundant catalyst. [ABSTRACT FROM AUTHOR]

Chiral-induced spin selectivity (CISS) effect provides innovative approach to spintronics and quantum-based devices for chiral materials. Different from the conventional ferromagnetic devices, the application of CISS effect is potential to operate under room temperature and zero applied magnetic field. Low dimensional chiral perovskites by introducing chiral amines are beginning to show significant CISS effect for spin injection, but research on chiral perovskites is still in its infancy, especially on spin-light emitting diode (spin-LED) construction. Here, the spin-QLEDs enabled by 2D chiral perovskites as CISS layer for spin-dependent carrier injection and CdSe/ZnS quantum dots (QDs) as light emitting layer are reported. The regulation pattern of the chirality and thickness of chiral perovskites, which affects the circularly polarized electroluminescence (CP-EL) emission of spin-QLED, is discovered. Notably, the spin injection polarization of 2D chiral perovskites is higher than 80% and the CP-EL asymmetric factor (g CP-EL ) achieves up to 1.6 × 10 -2 . Consequently, this work opens up a new and effective approach for high-performance spin-LEDs., (© 2023 Wiley-VCH GmbH.)

The chiral induced spin selectivity (CISS) effect in which selective transport of electron spins through helical chiral molecules occurs, has attracted a lot of attention in recent years. This effect was used to magnetize ferromagnetic (FM) samples by utilizing adsorbed chiral molecules. The electron transfer through the molecules was generated optically or electrically. In the optical configuration, circularly polarized light induced efficient magnetization by spin torque transfer (STT), using a hybrid of quantum dots (QDs) and chiral molecule self-assembled monolayer (SAM). Here, we use X-ray magnetic chiral dichroism (XMCD) spectroscopy in order to probe the optically induced magnetization on thin FM films. The results show differences in the FM magnetization depending on the optical circular polarization, matching previous non-local Hall probe measurements.

Highly efficient chirality resolution method and widely adaptive chirality sensor of ZnO nanorods (ZnONRs) decorated with multiple kinds of noble metal nanoparticles (NMNPs) by optically modulating angular momentum of electrons excitation are introduced. The enantiomers of glutamine functionalized different layers of NMNPs decorated ZnONRs can be easily recognized by modulating angular momentum of electron excitation controlled by the 405 nm, 532 nm, and 635 nm laser irradiations from the split currents in J-V curve. The improving sensitivity of multilayer NMNPs component is investigated, which exhibits the maximum spin polarization of L -glutamine functionalized one to four layer is 27.52 % under 532 nm, 27.81 % under 635 nm, and 26.53 % under 405 nm laser, showing over 1000 % enhancement compared to the one of bare ZnONRs. Above all, this sequence NMNPs component provide the variable selectivity to chirality resolution dependent on illumination environment, which takes few mins to do the purification of a specific amino acid by the novel transmittance measurement. • Chirality sensing via angular momentum controlling electrochemical system. • Multi-illumination application for chirality sensing and separation. • Imitation of energy transfer mechanism of chlorophyll. [ABSTRACT FROM AUTHOR]

The photoelectrochemical (PEC) water decomposition is a promising method to produce hydrogen from water. To improve the water decomposition efficiency of the PEC process, it is necessary to inhibit the generation of H 2 O 2 byproducts and reduce the overpotential required by cheap catalysts and a high current density. Studies have shown that coating the electrode with chiral molecules or chiral films can increase the hydrogen production and reduce the generation of H 2 O 2 byproducts. This is interpreted as the result of a chiral induced spin selectivity (CISS) effect, which induces a spin correlation between the electrons that are transferred to the anode. Here, we report the adsorption of chiral molecules onto titanium disulfide nanosheets. Firstly, titanium disulfide nanosheets were synthesized via thermal injection and then dispersed through ultrasonic crushing. This strategy combines the CISS with the plasma effect caused by the narrow bandgap of two-dimensional sulfur compounds to promote the PEC water decomposition with a high current density., (© 2022 Wiley-VCH GmbH.)

[Display omitted] • SPE modified with magnetic Fe 3 O 4 nanoparticles for the determination of Mn(II). • Magnetic field of Fe 3 O 4 nanoparticles increased mass transfer of Mn ions. • Increased net production of hydroxyl ions for electrodeposition of MnO 2. • Intermediate electron transfer enhanced by RGO. • Reduced deposition times using a disposable sensor. This study describes the robust modification of a screen-printed carbon electrode (SPE) for the magneto-electrochemical determination of Mn2+, in real soil samples, by square wave cathodic stripping voltammetry (SW-CSV). The carbon surface of a SPE was modified with electrodeposited Au, then dropcast with Fe 3 O 4 NPs functionalised with l -cysteine within a graphene oxide matrix. The magnetic Fe 3 O 4 NPs within the modification significantly increased the diffusion coefficient of the paramagnetic Mn2+ ion during deposition. Likewise, it also increased the number of hydroxyls available for the formation of the MnO 2 layer, attributed to chiral induced spin selectivity. The reduced graphene oxide (RGO) served to increase the surface area and heterogenous electron transfer rate of the intermediate reactions. The Au/ l -cys/Fe 3 O 4 /RGO modification displayed two significant improvements: enhancement of the Mn2+ response signal (212-fold increase) and improved flexibility for the analytical method (linear ranges from 0.5 to 300 µg L-1 to 62 – 1500 µg L-1 using deposition times of 300 or 30 s, respectively). Ten soil sample extracts were tested for Mn2+, by SW-CSV using the Au/ l -cys/Fe 3 O 4 /RGO modified SPE, and showed good agreement with FAAS, average error of 6.8%. [ABSTRACT FROM AUTHOR]

Chiral induced spin selectivity is a phenomenon that has been attributed to chirality, spin-orbit interactions, and nonequilibrium conditions, while the role of electron exchange and correlations have been investigated only marginally until very recently. However, as recent experiments show that chiral molecules acquire a finite spin-polarization merely by being in contact with a metallic surface, these results suggest that electron correlations play a more crucial role for the emergence of the phenomenon than previously thought. Here, it is demonstrated that molecular vibrations give rise to molecular charge redistribution and accompany spin-polarization when coupling a chiral molecule to a nonmagnetic metal. The presented theory opens up new routes to construct a comprehensive picture of enantiomer separation.

Recent studies on water‐splitting photoelectrochemical cells (PECs) have demonstrated the intriguing possibility of controlling the spin state in this chemical reaction to form H2 and O2 by exploiting the chirality of organic π‐conjugated supramolecular polymers. Although this fascinating phenomenon has been disclosed, the chiral supramolecular materials reported thus far are not optimized for acting as efficient photosensitizer for dye‐sensitized PECs. In this work we report on the design, synthesis, and characterization of chiral supramolecular aggregates based on C3‐symmetric triphenylamine‐based dyes that are able to both absorb visible light and control the spin state of the process. Variable temperature‐dependent spectroscopic measurements reveal the assembly process of the dyes and confirm the formation of chiral aggregates, both in solution as well as on solid supports. Photoelectrochemical measurements on TiO2‐based anodes validate the advantage of using chiral supramolecular aggregates as photosensitizer displaying higher photocurrent compared to achiral analogues. Moreover, fluorimetric tests for the quantification of the hydrogen peroxide produced, confirm the possibility of controlling the spin of the reaction exerting spin‐selection with chiral supramolecular polymers. These results represent a further step towards the next‐generation of organic‐based water‐splitting solar cells. [ABSTRACT FROM AUTHOR]

A general theory of the chiral induced spin selectivity (CISS) effect is presented. It is based on the fact that the spin-orbit (SO) coupling is small, a few meV, for the light atoms, which make up typical chiral molecules in experiments. We present a theorem based on the Onsager reciprocal principle, which states that the CISS effect vanishes when thermally averaging over all electron states. This zero result is avoided by the very nonthermal character of the incoming optically generated electrons in experimental realizations. Despite the small SO-coupling, the presence of accidental degeneracies in the molecular spectrum yields a sizable spin polarization. The CISS effect in the presence of magnetic leads is special. We prove that, in a situation with one magnetic lead, the other lead will become magnetized. This results from the interplay between the spin-orbit coupling in the chiral molecule and the magnetized lead. Numerical calculations for realistic chiral molecules confirm the theory.