Organic hierarchical branch micro/nanostructures constituted by single crystals with inherent multichannel characteristics exhibit superior potential in regulating photon transmission for photonic circuits. However, organic branch micro/nanostructures with precise branch positions are extremely difficult to achieve due to the randomness of the nucleation process. Herein, by taking advantage of the dislocation stress field-impurity interaction that solute molecules deposit preferentially along the dislocation line, twinning deformation was introduced into microcrystals to induce oriented nucleation sites, and ultimately organic branch microstructures with controllable branch sites were fabricated. The growth mechanism of these controllable single crystals with an angle of 140° between trunk and branch is attributed to the low lattice mismatching ratio (η) of 4.8%. These as-prepared hierarchical branch single crystals with asymmetrical optical waveguide characteristics have been demonstrated as an optical logic gate with multiple input/out channels, which provides a route to command the nucleation sites and offers potential applications in the organic optoelectronics at the micro/nanoscale.
The field of supramolecular metal-organic cage catalysis has grown rapidly in recent years. However, theoretical studies regarding the reaction mechanism and reactivity and selectivity controlling factors for supramolecular catalysis are still underdeveloped. Herein, we demonstrate a detailed density functional theory study on the mechanism, catalytic efficiency, and regioselectivity of the Diels-Alder reaction in bulk solution and within two [Pd6L4]12+ supramolecular cages. Our calculations are consistent with experiments. The origins of the catalytic efficiency of the bowl-shaped cage 1 have been elucidated to be the host-guest stabilization of the transition states and the favorable entropy effect. The reasons for the switch of the regioselectivity from 9,10-addition to 1,4-addition within the octahedral cage 2 were attributed to the confinement effect and the noncovalent interactions. This work would shed light on the understanding of [Pd6L4]12+ metallocage-catalyzed reactions and provide a detailed mechanistic profile otherwise difficult to obtain from experiments. The findings of this study could also aid to the improvement and development of more efficient and selective supramolecular catalysis.
Here, we report the first example of Ni-catalyzed asymmetric hydrosilylation of 1,1-disubstituted allenes with high level of regioselectivities and enantioselectivities. The key to achieve this stereoselective hydrosilylation reaction was the development of the SPSiOL-derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, and heterocycle tolerance, thus provides a versatile method for the construction of enantioenriched tertiary allylsilanes in a straightforward and atom-economic manner. DFT calculations were performed to reveal the reaction mechanism and the origins of the enantioselectivity.
Conventional laser cavities require discontinuity of material property or disorder to localize a light field for feedback. Recently, an emerging class of materials, twisted van der Waals materials, have been explored for applications in electronics and photonics. Here we propose and develop magic-angle lasers, where the localization is realized in periodic twisted photonic graphene superlattices. We reveal that the confinement mechanism of magic-angle lasers does not rely on a full bandgap but on the mode coupling between two twisted layers of photonic graphene lattice. Without any fine-tuning in structure parameters, a simple twist can result in nanocavities with strong field confinement and a high quality factor. Furthermore, the emissions of magic-angle lasers allow direct imaging of the wavefunctions of magic-angle states. Our work provides a robust platform to construct high-quality nanocavities for nanolasers, nano light-emitting diodes, nonlinear optics and cavity quantum electrodynamics at the nanoscale.
Spin-momentum locking is a direct consequence of bulk topological order and provides a basic concept to control a carrier's spin and charge flow for new exotic phenomena in condensed matter physics. However, up to date the research on spin-momentum locking solely focuses on its in-plane transport properties. Here, we report an emerging out-of-plane radiation feature of spin-momentum locking in a non-Hermitian topological photonic system and demonstrate a high performance topological vortex laser based on it. We find that the gain saturation effect lifts the degeneracy of the paired counterpropagating spin-momentum-locked edge modes enabling lasing from a single topological edge mode. The near-field spin and orbital angular momentum of the topological edge mode lasing has a one-to-one far-field radiation correspondence. The methodology of probing the near-field topology feature by far-field lasing emission can be used to study other exotic phenomena. The device can lead to applications in superresolution imaging, optical tweezers, free-space optical sensing, and communication.
Topological insulators are materials that behave as insulators in the bulk and as conductors at the edge or surface due to the particular configuration of their bulk band dispersion. However, up to date possible practical applications of this band topology on materials' bulk properties have remained abstract. Here, we propose and experimentally demonstrate a topological bulk laser. We pattern semiconductor nanodisk arrays to form a photonic crystal cavity showing topological band inversion between its interior and cladding area. In-plane light waves are reflected at topological edges forming an effective cavity feedback for lasing. This band-inversion-induced reflection mechanism induces single-mode lasing with directional vertical emission. Our topological bulk laser works at room temperature and reaches the practical requirements in terms of cavity size, threshold, linewidth, side-mode suppression ratio and directionality for most practical applications according to Institute of Electrical and Electronics Engineers and other industry standards. We believe this bulk topological effect will have applications in near-field spectroscopy, solid-state lighting, free-space optical sensing and communication.
