On the origins of life's homochirality: Inducing enantiomeric excess with spin-polarized electrons.

Life as we know it is homochiral, but the origins of biological homochirality on early Earth remain elusive. Shallow closed-basin lakes are a plausible prebiotic environment on early Earth, and most are expected to have significant sedimentary magnetite deposits. We hypothesize that ultraviolet (200- to 300-nm) irradiation of magnetite deposits could generate hydrated spin-polarized electrons sufficient to induce enantioselective prebiotic chemistry. Such electrons are potent reducing agents that drive reduction reactions where the spin polarization direction can enantioselectively alter the reaction kinetics. Our estimate of this chiral bias is based on the strong effective spin-orbit coupling observed in the chiral-induced spin selectivity (CISS) effect, as applied to energy differences in reduction reactions for different isomers. In the original CISS experiments, spin-selective electron transmission through a monolayer of double-strand DNA molecules is observed at room temperature-indicating a strong coupling between molecular chirality and electron spin. We propose that the chiral symmetry breaking due to the CISS effect, when applied to reduction chemistry, can induce enantioselective synthesis on the prebiotic Earth and thus facilitate the homochiral assembly of life's building blocks.

Twisted molecular wires polarize spin currents at room temperature.

A critical spintronics challenge is to develop molecular wires that render efficiently spin-polarized currents. Interplanar torsional twisting, driven by chiral binucleating ligands in highly conjugated molecular wires, gives rise to large near-infrared rotational strengths. The large scalar product of the electric and magnetic dipole transition moments ([Formula: see text]), which are evident in the low-energy absorptive manifolds of these wires, makes possible enhanced chirality-induced spin selectivity-derived spin polarization. Magnetic-conductive atomic force microscopy experiments and spin-Hall devices demonstrate that these designs point the way to achieve high spin selectivity and large-magnitude spin currents in chiral materials.

Persistent Chirality-Induced Spin-Selectivity Effect in Circular Helix Molecules.

The spin-orbit coupling (SOC), the dynamics of the nonequilibrium transport process, and the breaking of time-reversal and space-inversion symmetries have been regarded as key factors for the emergence of chirality-induced spin selectivity (CISS) and chirality-dependent spin currents in helix molecules. In this work, we demonstrated the generation of persistent CISS currents in various circular single-stranded DNAs and 310-helix proteins for the first time, regardless of whether an external magnetic flux is applied or not. This new CISS effect presents only in equilibrium transport processes, distinct from the traditional CISS observed in nonequilibrium transport processes and linear helix molecules; we term it as the PCISS effect. Notably, PCISS manifests irrespective of whether the SOC is chirality-driven or stems from heavy-metal substrates, making it an efficient way to generate chirality-locked pure spin currents. Our research establishes a novel paradigm for examining the underlying physics of the CISS effect.

Electron Spin Polarization and Memory Effect in Supramolecular Gel Exclusively From Achiral Building Blocks.

Chirality has been identified as a crucial component in achieving high spin selectivity in organic polymers and π-conjugated molecules. In particular, chiral polymers and supramolecular structures have emerged as promising candidates for spin filtering due to the chirality-induced spin selectivity (CISS) effect. However, the CISS effect in supramolecular systems has not been extensively investigated, despite its potential for applications in spintronics. In this work, for the first time, the potential applications of the CISS effect in supramolecular gel materials and shed light on its untapped possibilities have been successfully explored. The ability of supramolecular gel exclusively made from achiral building blocks to selectively filter electron's spin through the symmetry breaking has been demonstrated. Furthermore, this study shows that their spin filtering efficacy can be improved by using chiral solvents. More importantly, the CISS effect has been employed to explore a novel phenomenon referred to as the "spin memory effect", where the desired spin information is preserved by retaining the helicity even in the absence of the chiral solvent. These findings underscore the immense potential for spintronics applications that rely solely on achiral components, thereby paving the way for new possibilities in device design and functionality.

Unconventional approaches for chiral resolution.

Chirality is a fundamental and ubiquitous property of nature involved in multiple fields of science. In particular, the possible resolution of the enantiomeric forms of a molecule is crucial in the pharmaceutical, food, and agrochemical industries. The search for efficient, broad-spectrum, and yet simple methods for obtaining enantiomerically pure substances is a current challenge. Enantioselective resolution methods rely on an asymmetric environment that allows the two antipodes of a chiral molecule to be distinguished. In addition to enantiomeric separation techniques, such as chromatography and electrophoresis, new promising approaches involving out-of-the-scheme synergistic effects between chiral selectors (CS) and external stimuli are emerging. This Trends article discusses different enantioselective mechanisms triggered by unconventional physicochemical stimuli for the design of avant-garde approaches that could offer novel perspectives in the field of chiral resolution.

Electron Spin-Dependent Electrocatalysis for the Oxygen Reduction Reaction in a Chiro-Self-Assembled Iron Phthalocyanine Device.

The chiral-induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin-dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well-known molecular catalyst for this reaction. The FePc complex belongs to the non-precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self-assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro-self-assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides' handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D-enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2 /H2 O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L-enantiomers.

Dual Signature of Chirality Induced Spin Selectivity through Spontaneous Resolution of 2D Metal-Organic Frameworks.

The Chiral-Induced Spin Selectivity (CISS) effect has emerged as a fascinating phenomenon within the realm of electron's spin manipulation, showcasing a unique interplay between electron's spin and molecular chirality. Subsequent to its discovery, researchers have been actively involved in exploring the new chiral molecules as effective spin filters. In the realm of observing the CISS effect, the conventional approach has mandated the utilization of two distinct enantiomers of chiral molecules. However, this present study represents a significant advancement by demonstrating the ability to control both spin states of electrons in a single system. In this work, we have demonstrated the preparation of chiral metal-organic frameworks (MOFs) via a "spontaneous resolution" process, obviating the requirement for chiral sources. Remarkably, this work signifies the first instance of achieving dual signature of spin selectivity from a single and exclusively achiral system through a spontaneous resolution process. This holds immense potential as it facilitates the production of two distinct spin-filtering materials from a unified system. In overall, the significant findings achieved using these robust and easily synthesized MOF crystals without the requirement for chiral medium represent a crucial advancement in enhancing the effectiveness of spin filtering materials to produce spintronic devices.

Spin-Selective Electron Transport Through Single Chiral Molecules.

The interplay between chirality and magnetism is a source of fascination among scientists for over a century. In recent years, chirality-induced spin selectivity (CISS) has attracted renewed interest. It is observed that electron transport through layers of homochiral molecules leads to a significant spin polarization of several tens of percent. Despite the abundant experimental evidence gathered through mesoscopic transport measurements, the exact mechanism behind CISS remains elusive. This study reports spin-selective electron transport through single helical aromatic hydrocarbons that are sublimed in vacuo onto ferromagnetic cobalt surfaces and examined with spin-polarized scanning tunneling microscopy (SP-STM) at a temperature of 5 K. Direct comparison of two enantiomers under otherwise identical conditions revealed magnetochiral conductance asymmetries of up to 50% when either the molecular handedness is exchanged or the magnetization direction of the STM tip or Co substrate is reversed. Importantly, the results rule out electron-phonon coupling and ensemble effects as primary mechanisms responsible for CISS.

Challenges in the Direct Detection of Chirality-induced Spin Selectivity: Investigation of Foldamer-based Donor-acceptor Dyads.

Over the past two decades, the chirality-induced spin selectivity (CISS) effect was reported in several experiments disclosing a unique connection between chirality and electron spin. Recent theoretical works highlighted time-resolved Electron Paramagnetic Resonance (trEPR) as a powerful tool to directly detect the spin polarization resulting from CISS. Here, we report a first attempt to detect CISS at the molecular level by linking the pyrene electron donor to the fullerene acceptor with chiral peptide bridges of different length and electric dipole moment. The dyads are investigated by an array of techniques, including cyclic voltammetry, steady-state and transient optical spectroscopies, and trEPR. Despite the promising energy alignment of the electronic levels, our multi-technique analysis reveals no evidence of electron transfer (ET), highlighting the challenges of spectroscopic detection of CISS. However, the analysis allows the formulation of guidelines for the design of chiral organic model systems suitable to directly probe CISS-polarized ET.

Atomic and Molecular Layer Deposition of Chiral Thin Films Showing up to 99% Spin Selective Transport.

Spin electronics is delivering a much desired combination of properties such as high speed, low power, and high device densities for the next generation of memory devices. Utilizing chiral-induced spin selectivity (CISS) effect is a promising path toward efficient and simple spintronic devices. To be compatible with state-of-the-art integrated circuits manufacturing methodologies, vapor phase methodologies for deposition of spin filtering layers are needed. Here, we present vapor phase deposition of hybrid organic-inorganic thin films with embedded chirality. The deposition scheme relies on a combination of atomic and molecular layer deposition (A/MLD) utilizing enantiomeric pure alaninol molecular precursors combined with trimethyl aluminum (TMA) and water. The A/MLD deposition method deliver highly conformal thin films allowing the fabrication of several types of nanometric scale spintronic devices. The devices showed high spin polarization (close to 100%) for 5 nm thick spin filter layer deposited by A/MLD. The procedure is compatible with common device processing methodologies.

Role of Exchange Interactions in the Magnetic Response and Intermolecular Recognition of Chiral Molecules.

The physical origin of the so-called chirality-induced spin selectivity (CISS) effect has puzzled experimental and theoretical researchers over the past few years. Early experiments were interpreted in terms of unconventional spin-orbit interactions mediated by the helical geometry. However, more recent experimental studies have clearly revealed that electronic exchange interactions also play a key role in the magnetic response of chiral molecules in singlet states. In this investigation, we use spin-polarized closed-shell density functional theory calculations to address the influence of exchange contributions to the interaction between helical molecules as well as of helical molecules with magnetized substrates. We show that exchange effects result in differences in the interaction properties with magnetized surfaces, shedding light into the possible origin of two recent important experimental results: enantiomer separation and magnetic exchange force microscopy with AFM tips functionalized with helical peptides.

Differential Charging in Photoemission from Mercurated DNA Monolayers on Ferromagnetic Films.

Spin-dependent and enantioselective electron-molecule scattering occurs in photoelectron transmission through chiral molecular films. This spin selectivity leads to electron spin filtering by molecular helices, with increasing magnitude concomitant with increasing numbers of helical turns. Using ultraviolet photoelectron spectroscopy, we measured spin-selective surface charging accompanying photoemission from ferromagnetic substrates functionalized with monolayers of mercurated DNA hairpins that constitute only one helical turn. Mercury ions bind specifically at thymine-thymine mismatches within self-hybridized single-stranded DNA, enabling precise control over the number and position of Hg2+ along the helical axis. Differential charging of the organic layers, manifested as substrate-magnetization-dependent photoionization energies, was observed for DNA hairpins containing Hg2+; no differences were measured for hairpin monolayers in the absence of Hg2+. Inversion of the DNA helical secondary structure at increased metal loading led to complementary inversion in spin selectivity. We attribute these results to increased scattering probabilities from relativistic enhancement of spin-orbit interactions in mercurated DNA.

An Ideal Spin Filter: Long-Range, High-Spin Selectivity in Chiral Helicoidal 3-Dimensional Metal Organic Frameworks.

An enantiopure, conductive, and paramagnetic crystalline 3-D metal-organic framework (MOF), based on Dy(III) and the l-tartrate chiral ligand, is proved to behave as an almost ideal electron spin filtering material at room temperature, transmitting one spin component only, leading to a spin polarization (SP) power close to 100% in the ±2 V range, which is conserved over a long spatial range, larger than 1 µm in some cases. This impressive spin polarization capacity of this class of nanostructured materials is measured by means of magnetically polarized conductive atomic force microscopy and is attributed to the Chirality-Induced Spin Selectivity (CISS) effect of the material arising from a multidimensional helicity pattern, the inherited chirality of the organic motive, and the enhancing influence of Dy(III) ions on the CISS effect, with large spin-orbit coupling values. Our results represent the first example of a MOF-based and CISS-effect-mediated spin filtering material that shows a nearly perfect SP. These striking results obtained with our robust and easy-to-synthesize chiral MOFs constitute an important step forward in to improve the performance of spin filtering materials for spintronic device fabrication.

Chiral Nematic Cellulose Nanocrystal Films for Enhanced Charge Separation and Quantum-Confined Stark Effect.

Efficient charge separation is essential in various optoelectronic systems, yet it continues to pose substantial challenges. Building upon the recent evidence that chiral biomolecules can function as electron spin filters, this study aims to extend the application of chirality-driven charge separation from the molecular level to the mesoscale and supramolecular scale. Utilizing cellulose nanocrystals (CNCs) derived from cellulose, the most abundant biomaterial on Earth, this research leverages their self-assembly into chiral nematic structures and their dielectric properties. A device is introduced featuring a chiral nematic hybrid film composed of CNCs and quantum dots (QDs), decorated with iron oxide nanoparticles. Using the quantum-confined Stark effect (QCSE) to probe charge separation, we reveal significant sensitivity to the circular polarization of light and the chiral nematic structure of the film. This approach achieves effective, long-lasting charge separation, both locally and across length scales exceeding 1 µm, enabling potential applications such as self-assembled devices that combine photovoltaic cells with electric capacitance as well as optical electric-field hybrid biosensors.

Efficient Spin-Selective Electron Transport at Low Voltages of Thia-Bridged Triarylamine Hetero[4]helicenes Chemisorbed Monolayer.

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.

Chirality Versus Symmetry: Electron's Spin Selectivity in Nonpolar Chiral Lead-Bromide Perovskites.

In the last decade, chirality-induced spin selectivity (CISS), the spin-selective electron transport through chiral molecules, has been described in a large range of materials, from insulators to superconductors. Because more experimental studies are desired for the theoretical understanding of the CISS effect, chiral metal-halide semiconductors may contribute to the field thanks to their chiroptical and spintronic properties. In this regard, this work uses new chiral organic cations S-HP1A and R-HP1A (HP1A = 2-hydroxy-propyl-1-ammonium) to prepare 2D chiral halide perovskites (HPs) which crystallize in the enantiomorphic space groups P43 21 2 and P41 21 2, respectively. The fourfold symmetry induces antiferroelectricity along the stacking axis which, combined to incomplete Rashba-like splitting in each individual 2D polar layer, results in rare spin textures in the band structure. As revealed by magnetic conductive-probe atomic force microscopy (AFM) measurements, these materials show CISS effect with partial spin polarization (SP; ±40-45%). This incomplete effect is efficient enough to drive a chiro-spintronic device as demonstrated by the fabrication of spin valve devices with magnetoresistance (MR) responses up to 250 K. Therefore, these stable lead-bromide HP materials not only represent interesting candidates for spintronic applications but also reveal the importance of polar symmetry-breaking topology for spin selectivity.

Chiral Van Der Waals Superlattices for Enhanced Spin-Selective Transport and Spin-Dependent Electrocatalytic Performance.

The emergence of the chiral-induced spin-selectivity (CISS) effect offers a new avenue for chiral organic molecules to autonomously manipulate spin configurations, thereby opening up possibilities in spintronics and spin-dependent electrochemical applications. Despite extensive exploration of various chiral systems as spin filters, one often encounters challenges in achieving simultaneously high conductivity and high spin polarization (SP). In this study, a promising chiral van der Waals superlattice, specifically the chiral TiS2 crystal, is synthesized via electrochemical intercalation of chiral molecules into a metallic TiS2 single crystal. Multiple tunneling processes within the highly ordered chiral layered structure of chiral TiS2 superlattices result in an exceptionally high SP exceeding 90%. This remarkable observation of significantly high SP within the linear transport regime is unprecedented. Furthermore, the chiral TiS2 electrode exhibits enhanced catalytic activity for oxygen evolution reaction (OER) due to its remarkable spin-selectivity for triplet oxygen evolution. The OER performance of chiral TiS2 superlattice crystals presented here exhibits superior characteristics to previously reported chiral MoS2 catalysts, with an approximately tenfold increase in current density. The combination of metallic conductivity and high SP sets the stage for the development of a new generation of CISS materials, enabling a wide range of electron spin-based applications.

Hybrid Chiral MoS2 Layers for Spin-Polarized Charge Transport and Spin-Dependent Electrocatalytic Applications.

The chiral-induced spin selectivity effect enables the application of chiral organic materials for spintronics and spin-dependent electrochemical applications. It is demonstrated on various chiral monolayers, in which their conversion efficiency is limited. On the other hand, relatively high spin polarization (SP) is observed on bulk chiral materials; however, their poor electronic conductivities limit their application. Here, the design of chiral MoS2 with a high SP and high conductivity is reported. Chirality is introduced to the MoS2 layers through the intercalation of methylbenzylamine molecules. This design approach activates multiple tunneling channels in the chiral layers, which results in an SP as high as 75%. Furthermore, the spin selectivity suppresses the production of H2 O2 by-product and promotes the formation of ground state O2 molecules during the oxygen evolution reaction. These potentially improve the catalytic activity of chiral MoS2 . The synergistic effect is demonstrated as an interplay of the high SP and the high catalytic activity of the MoS2 layer on the performance of the chiral MoS2 for spin-dependent electrocatalysis. This novel approach employed here paves way for the development of other novel chiral systems for spintronics and spin-dependent electrochemical applications.

The Importance of Spin State in Chiral Supramolecular Electronics.

The field of spintronics explores how magnetic fields can influence the properties of organic and inorganic materials by controlling their electron's spins. In this sense, organic materials are very attractive since they have small spin-orbit coupling, allowing long-range spin-coherence over times and distances longer than in conventional metals or semiconductors. Usually, the small spin-orbit coupling means that organic materials cannot be used for spin injection, requiring ferromagnetic electrodes. However, chiral molecules have been demonstrated to behave as spin filters upon light illumination in the phenomenon described as chirality-induced spin selectivity (CISS) effect. This means that electrons of certain spin can go through chiral assemblies of molecules preferentially in one direction depending on their handedness. This is possible because the lack of inversion symmetry in chiral molecules couples with the electron's spin and its linear momentum so the molecules transmit the one preferred spin. In this respect, chiral semiconductors have great potential in the field of organic electronics since when charge carriers are created, a preferred spin could be transmitted through a determined handedness structure. The exploration of the CISS effect in chiral supramolecular semiconductors could add greatly to the efforts made by the organic electronics community since charge recombination could be diminished and charge transport improved when the spins are preferentially guided in one specific direction. This review outlines the advances in supramolecular chiral semiconductors regarding their spin state and its influence on the final electronic properties.

Multistate Switching of Spin Selectivity in Electron Transport through Light-Driven Molecular Motors.

It is established that electron transmission through chiral molecules depends on the electron's spin. This phenomenon, termed the chiral-induced spin selectivity (CISS), effect has been observed in chiral molecules, supramolecular structures, polymers, and metal-organic films. Which spin is preferred in the transmission depends on the handedness of the system and the tunneling direction of the electrons. Molecular motors based on overcrowded alkenes show multiple inversions of helical chirality under light irradiation and thermal relaxation. The authors found here multistate switching of spin selectivity in electron transfer through first generation molecular motors based on the four accessible distinct helical configurations, measured by magnetic-conductive atomic force microscopy. It is shown that the helical state dictates the molecular organization on the surface. The efficient spin polarization observed in the photostationary state of the right-handed motor coupled with the modulation of spin selectivity through the controlled sequence of helical states, opens opportunities to tune spin selectivity on-demand with high spatio-temporal precision. An energetic analysis correlates the spin injection barrier with the extent of spin polarization.