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Summary The photomagnetic effect is known to be related only to transition metal atoms with empty orbitals and spin-state changes. In general, noble metals with high electron density cannot be used as photomagnetic materials because of the absence of spin polarization. However, here, we found that photomagnetic-chiral anisotropy (PM-ChA) was generated in chiral nanostructured Au films (CNAFs), and opposite photomagnetic fields (PMFs) were created in the antipodal CNAFs under unpolarized irradiation. The PM-ChA was speculated to arise from directional alignment of opposite spins polarized by the asymmetric spin-orbit coupling due to the opposite effective magnetic fields induced by electron motion in the antipodal helical structure. PM-ChA can be applied in enantiomeric quantification, probably because of the spin polarization coupling between CNAFs and enantiomers. PM-ChA of noble metals generated by directional spin control in helical nanostructures could provide new strategies in quantum technology and theories in magnetophysics.

Summary The enantiomeric excess phenomenon in spontaneous chiral symmetry breaking (SCSB) is a crucial issue in the origin of homochirality in nature, whereas chiral inorganic compounds have long been reckoned as racemates. Here, we report the SCSB in the self-assembly of cadmium chalcogenide nanorods, leading to chiral biases away from the racemate. In the presence of achiral organics, helical CdSe@CdS nanorods (HCCNs) with unidirectionally rotated crystal lattices along the rod axis were stochastically formed on the epitaxial interface of the {111}cub/{0001}hex planes. The stability of helical dislocation structures, as supported by a theoretical analysis of their binding energies, suggested the possibility of the emergence of helical structures in an achiral environment. Hierarchical chiral films induced by simple solvent evaporation self-assembly of HCCNs exhibited spontaneous enantiomeric excess between batches, which was speculated to be originated from the enantiomeric excess seed assembly that induce one-handedness dominated system based on the majority rules.

Half-metallic materials are theoretically predicted to be metallic and insulating, which have not been confirmed experimentally, and the predictions are still in doubt. We report the resistance-chiral anisotropy (R-ChA), i.e., chirality-dependent electrical conductivity, in chiral mesostructured Fe3 O4 films (CMFFs) grown on the substrates via a hydrothermal method using amino acids as symmetry-breaking agents. Two levels of chirality exist in the CMFFs: primary distortion of the crystal lattice forms twisted nanoflakes, and secondary helical stacking of nanoflakes forms fan-shaped nanoplates. At temperatures below 30 K, the CMFFs exhibited metallic conductivity and insulation for one handedness and the other, respectively. The chirality-dependent effective magnetic fields were speculated to stabilize the opposite spin in the antipodal chiral frame, which led to the free transport of electrons in one handedness of the chiral structure and immobility for the other handedness.

Spin polarisation is found in the centrosymmetric nonferromagnetic crystals, chiral mesostructured NiO films (CMNFs), fabricated through the symmetry-breaking effect of a chiral molecule. Two levels of chirality were identified: primary nanoflakes with atomically twisted crystal lattices and secondary helical stacking of the nanoflakes. Spin polarisation of the CMNFs was confirmed by chirality-dependent magnetic-tip conducting atomic force microscopy (mc-AFM) and magnetic field-independent magnetic circular dichroism (MCD). Electron transfer in the symmetry-breaking electric field was speculated to create chirality-dependent effective magnetic fields. The asymmetric spin-orbit coupling (SOC) generated by effective magnetic fields selectively modifies the opposite spin motion in the antipodal CMNFs. Our findings provide fundamental insights for directional spin control in unprecedented functional inorganic materials.

Chiral mesostructures exhibit distinctive twisting and helical hierarchical stacking ranging from atomic to micrometre scales with fascinating structural-chiral anisotropy properties. However, the detailed determination of their multilevel chirality remains challenging due to the limited information from spectroscopy, diffraction techniques, scanning electron microscopy and the two-dimensional projections in transmission electron microscopy. Herein, we report a general approach to determine chiral hierarchical mesostructures based on three-dimensional electron diffraction tomography (3D EDT), by which the structure can be solved synchronously according to the quantitative measurement of diffraction spot deformations and their arrangement in reciprocal space. This method was verified on two samples—chiral mesostructured nickel molybdate and chiral mesostructured tin dioxide—revealing hierarchical chiral structures that cannot be determined by conventional techniques. This approach provides more precise and comprehensive identification of the hierarchical mesostructures, which is expected to advance our understanding of structural–chiral anisotropy at the fundamental level.

Spin selectivity physically depends on either magnetic materials with strong internal magnetic fields or symmetry-breaking materials with large spin-orbit coupling (SOC). However, the spin selectivity of symmetry-breaking magnetic materials is not understood. Herein, the spin selectivity of iron oxides with different magnetisms arising from varying spin alignment is investigated. Chiral mesostructured films of Fe

Chiral molecule-driven asymmetric structures are known to be elusive because of the intriguing chirality transfer from chiral molecules to achiral species. Here, we found that the chiral assembly of BiOBr is independent of the chirality of the organic molecular inducer but dependent on geometric structural matching between the inducer and inorganic species. Diastereoisomeric sugar alcohols (DSAs) with identical numbers of carbon chiral centers and functional groups but with different

Chiral mesoporous silica ribbons and rods with inversed handedness have been synthesized with the same enantio pure N-acylaminoacidat temperatures of 0 °C and 20 °C, respectively. With involving Cu2+ and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) as probes, ribbons and rods revealed opposite signals in diffuse-reflectance circular dichroism (DRCD) spectra, indicating the existence of inversed supramolecular chiral imprintings through helical stacking of amphiphiles. The structural evolution was systematically studied by the freeze-dried products sampled at different time after the addition of silica precursors. The H-bonding-depended molecular orientation probably controls the chiral sense upon forming chiral molecular stacking, which would be the origin of such handedness inversion phenomenon

Mesostructured fluorescent silica hybrids (MFSHs) were synthesized using tetraphenylethylene (TPE)-based quaternary ammonium salts as amphiphilic organic fluorophore templates, carboxyethylsilanetriol disodium salt (CES) as a co-structure directing agent (CSDA) and tetraethylorthosilicate (TEOS) as an inorganic precursor. With increasing alkyl chain length of the templates, the mesostructures transformed from a lamellar structure (alkyl carbon chains of C4, C5, C6 and C7) to three-dimensional (3D) bicontinuous cubic gyroid structures (C8 and C10). These materials show typical aggregation-induced emission (AIE) behaviours corresponding to the molecular arrangement in the mesoscale. Compared to the pure template, the emission maximum of the material with a lamellar structure shows a red-shift phenomenon due to the higher conjugation caused by the close stacking of the AIEgens, while the emission maximum remains unchanged in the bicontinuous cubic structure owing to the loose stacking of the template molecules.

Antipodal chiral AIEgen-silica hybrid mesostructures were fabricated by spontaneous chiral self-assembly of the achiral amphiphilic AIEgen 2-[4-(1,2,2-triphenylethenyl)phenoxy]-acetic acid via a co-structure directing route in the absence of any symmetry-breaking agent. The produced AIEgen-silica hybrid mesostructured nanotubes showed chiral features with optical activity originating from J-aggregation with an excess of one stereochemical hand of the helical conformation of the AIEgen.

Achieving strong and broadband circularly polarized colour responses in chiral inorganic materials is challenging. Here, we fabricated chiral mesostructured bismuth oxybromide (BiOBr) films (CMBFs) via hydrothermal growth using chiral sugar alcohols as symmetry-breaking agents. The layered slabs of BiOBr crystals with weak van-der-Waals interactions are prone to mismatching due to the chiral driving force, resulting in hierarchically chiral arrangements of fine size. Three levels of chirality exist in the CMBFs: primary, helical distortion crystal lattices of a nanoflake, secondary, helical stacking of nanoflakes to form nanoplates, and tertiary, chiral vortexes arranged by nanoplates. The CMBFs displayed optical activities (OAs) over a wide wavelength range of 350-2500 nm with an anisotropic factor of up to 0.99, which led to a significant chirality-dependent colour response to circularly polarized light. The high selectivity can be considered as the result of enhanced resonance due to structural-handedness matching and the synergistic effect of multiple OAs.

A surface-enhanced Raman scattering-chiral anisotropy (SERS-ChA) effect is reported that combines chiral discrimination and surface Raman scattering enhancement on chiral nanostructured Au films (CNAFs) equipped in the normal Raman scattering Spectrometer. The CNAFs provided remarkably higher enhancement factors of Raman scattering (EFs) for particular enantiomers, and the SERS intensity was proportional to the enantiomeric excesses (ee) values. Except for molecules with mesomeric species, all of the tested enantiomers exhibited high SERS-ChA asymmetry factors (g), ranging between 1.34 and 1.99 regardless of polarities, sizes, chromophores, concentrations and ee. The effect might be attributed to selective resonance coupling between the induced electric and magnetic dipoles associated with enantiomers and chiral plasmonic modes of CNAFs.

Chiral mesostructured TiO2 films (CMTFs) were synthesized by a hydrothermal method using L/D-mannitol as the symmetry-breaking agent and titanium foil as both the substrate and inorganic precursor. Five levels of hierarchical chirality exist in the CMTFs, exhibiting optical activity (OA) at ∼350 nm attributed to the electronic transitions in a dissymmetric electric field.

Screw-like hierarchical chiral fibres were constructed by co-templating two building tectons, DNA and porphyrin, under the bridging effect of cationic organosilane. The chirality transfer from the DNA molecule to meso-tetra(4-sulfonatophenyl)porphyrin assemblies in turn affected the subsequent arrangement of DNA assemblies, thus indicating a multi-dimensional hierarchical chiral amplification process from the molecular scale to the macroscopic scale.

A macroporous silica with azimuthally shifted double-diamond frameworks has been synthesized by the self-assembly of an amphiphilic ABC triblock terpolymer poly(tert-butyl acrylate)-b-polystyrene-b-poly(ethylene oxide) and silica source in a mixture of tetrahydrofuran and water. The structure of the macroporous silica consists of a porous system separated by two sets of hollow double-diamond frameworks shifted 0.25c along ⟨001⟩ and adhered to each other crystallographically due to the loss of the mutual support in the unique synthesis, forming a tetragonal structure (space group I41/amd). The unit cell parameter was changed from a = 168 to ∼240 nm with c = √2a by tuning the synthesis condition and the wide edge of the macropore size was ∼100 to ∼140 nm. Electron crystallography was applied to solve the structure. Our studies demonstrate electron crystallography is the only way to solve the complex structure in such length scale. Besides, this structure exhibits structural color that ranged from violet to ...

Helical symmetry can be found in most flowers with a rotation of contort petal aestivation. For micro- and nanoscale analogies, flower mimicking structures have been reproduced; however, the conceptual chirality of “nanoflowers” has not yet been defined. Here, the chirality of the “flower” was defined by its nanosized chiral structure and consequent optical activity (OA), opening new horizons for the physical theory and chiral materials. We report the surfactant-mediated hydrothermal synthesis of chiral CuO nanoflowers using sodium dodecyl sulfate (SDS) as a structure-directing agent, an amino alcohol as a symmetry-breaking agent, and cupric salt as the inorganic source. Two levels of hierarchical chirality exist for a CuO nanoflower including primary helically arranged “nanoflakes” and secondary helical “subnanopetals” that form “nanopetals”. The nanoflowers exhibited a prominent optical response to circularly polarized light (CPL) at the absorption bands characteristic of CuO.

Chiral metal oxide complexes with tunable optical response to circularly polarised light over the full range of the UV-Vis absorption band were synthesised. This optical activity was attributed to electronic transitions from the ground state to the excited state or from the valence band to the conduction band under an asymmetric electric field.

The optical chirality induced at the absorption bands due to electronic exciton coupling of the transition dipole moments between chromophores in close proximity is ubiquitous in helical organic materials. However, inorganic materials with optical activity resulting from electronic transitions have not been explored. Here we report the synthesis of chiral TiO2 fibres via transcription of the helical structure of amino acid-derived amphiphile fibres through coordination bonding interactions between the organics and the TiO2 source. Upon calcination, the as-prepared amorphous TiO2 double-helical fibres with a pitch length of ~100 nm were converted to double-helical crystalline fibres with stacks of anatase nanocrystals in an epitaxial helical relationship. Both the amorphous and anatase crystalline helical TiO2 fibres exhibited optical response to circularly polarized light at the absorption edge around ~350 nm. This was attributed to the semiconductor TiO2-based electronic transitions from the valence band to the conduction band under an asymmetric electric field., Optical activity resulting from electronic transitions in chiral inorganic materials is rare. Liu et al. report the synthesis of amino acid-derived amphiphile templated chiral TiO2 fibres, which exhibit an optical response to polarized light resulting from valence to conduction band electronic transitions.