Molecular Face-Rotating Cube with Emergent Chiral and Fluorescence Properties

Chiral cage compounds are mainly constructed from chiral precursors or based on the symmetry breaking during coordination-driven self-assembly. Herein, we present a strategy to construct chiral organic cages by restricting the <i>P</i> or <i>M</i> rotational configuration of tetraphenylethylene (TPE) faces through dynamic covalent chemistry. The combination of graph theory, experimental characterizations and theoretical calculations suggests emergent chirality of cages is originated from complex arrangements of TPE faces with different orientational and rotational configurations. Accompanied by the generation of chirality, strong fluorescence also emerged during cage formation, even in dilute solutions with various solvents. In addition, the circularly polarized luminescence of the cages is realized as a synergy of their dual chiral and fluorescence properties. Chirality and fluorescence of cages are remarkably stable, because intramolecular flipping of phenyl rings in TPE faces is restricted, as indicated by calculations. This study provides insight into construct chiral cages by the rational design through graph theory, and might facilitate further design of cages and other supramolecular assemblies from aggregation-induced emission active building blocks

Three-Dimensional and Time-Ordered Surface-Enhanced Raman Scattering Hotspot Matrix

The “fixed” or “flexible” design of plasmonic hotspots is a frontier area of research in the field of surface-enhanced Raman scattering (SERS). Most reported SERS hotspots have been shown to exist in zero-dimensional point-like, one-dimensional linear, or two-dimensional planar geometries. Here, we demonstrate a novel three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, simply achieved by evaporating a droplet of citrate-Ag sols on a fluorosilylated silicon wafer. In situ synchrotron-radiation small-angle X-ray scattering (SR-SAXS), combined with dark-field microscopy and in situ micro-UV, was employed to explore the evolution of the 3D geometry and plasmonic properties of Ag nanoparticles in a single droplet. In such a droplet, there is a distinct 3D geometry with minimal polydispersity of particle size and maximal uniformity of interparticle distance, significantly different from the dry state. According to theoretical simulations, the liquid adhesive force promotes a closely packed assembly of particles, and the interparticle distance is not fixed but can be balanced in a small range by the interplay of the van der Waals attraction and electrostatic repulsion experienced by a particle. The “trapping well” for immobilizing particles in 3D space can result in a large number of hotspots in a 3D geometry. Both theoretical and experimental results demonstrate that the 3D hotspots are predictable and time-ordered in the absence of any sample manipulation. Use of the matrix not only produces giant Raman enhancement at least 2 orders of magnitude larger than that of dried substrates, but also provides the structural basis for trapping molecules. Even a single molecule of resonant dye can generate a large SERS signal. With a portable Raman spectrometer, the detection capability is also greatly improved for various analytes with different natures, including pesticides and drugs. This 3D hotspot matrix overcomes the long-standing limitations of SERS for the ultrasensitive characterization of various substrates and analytes and promises to transform SERS into a practical analytical technique

Three-Dimensional and Time-Ordered Surface-Enhanced Raman Scattering Hotspot Matrix

The “fixed” or “flexible” design of plasmonic hotspots is a frontier area of research in the field of surface-enhanced Raman scattering (SERS). Most reported SERS hotspots have been shown to exist in zero-dimensional point-like, one-dimensional linear, or two-dimensional planar geometries. Here, we demonstrate a novel three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, simply achieved by evaporating a droplet of citrate-Ag sols on a fluorosilylated silicon wafer. In situ synchrotron-radiation small-angle X-ray scattering (SR-SAXS), combined with dark-field microscopy and in situ micro-UV, was employed to explore the evolution of the 3D geometry and plasmonic properties of Ag nanoparticles in a single droplet. In such a droplet, there is a distinct 3D geometry with minimal polydispersity of particle size and maximal uniformity of interparticle distance, significantly different from the dry state. According to theoretical simulations, the liquid adhesive force promotes a closely packed assembly of particles, and the interparticle distance is not fixed but can be balanced in a small range by the interplay of the van der Waals attraction and electrostatic repulsion experienced by a particle. The “trapping well” for immobilizing particles in 3D space can result in a large number of hotspots in a 3D geometry. Both theoretical and experimental results demonstrate that the 3D hotspots are predictable and time-ordered in the absence of any sample manipulation. Use of the matrix not only produces giant Raman enhancement at least 2 orders of magnitude larger than that of dried substrates, but also provides the structural basis for trapping molecules. Even a single molecule of resonant dye can generate a large SERS signal. With a portable Raman spectrometer, the detection capability is also greatly improved for various analytes with different natures, including pesticides and drugs. This 3D hotspot matrix overcomes the long-standing limitations of SERS for the ultrasensitive characterization of various substrates and analytes and promises to transform SERS into a practical analytical technique

Three-Dimensional and Time-Ordered Surface-Enhanced Raman Scattering Hotspot Matrix

The “fixed” or “flexible” design of plasmonic hotspots is a frontier area of research in the field of surface-enhanced Raman scattering (SERS). Most reported SERS hotspots have been shown to exist in zero-dimensional point-like, one-dimensional linear, or two-dimensional planar geometries. Here, we demonstrate a novel three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, simply achieved by evaporating a droplet of citrate-Ag sols on a fluorosilylated silicon wafer. In situ synchrotron-radiation small-angle X-ray scattering (SR-SAXS), combined with dark-field microscopy and in situ micro-UV, was employed to explore the evolution of the 3D geometry and plasmonic properties of Ag nanoparticles in a single droplet. In such a droplet, there is a distinct 3D geometry with minimal polydispersity of particle size and maximal uniformity of interparticle distance, significantly different from the dry state. According to theoretical simulations, the liquid adhesive force promotes a closely packed assembly of particles, and the interparticle distance is not fixed but can be balanced in a small range by the interplay of the van der Waals attraction and electrostatic repulsion experienced by a particle. The “trapping well” for immobilizing particles in 3D space can result in a large number of hotspots in a 3D geometry. Both theoretical and experimental results demonstrate that the 3D hotspots are predictable and time-ordered in the absence of any sample manipulation. Use of the matrix not only produces giant Raman enhancement at least 2 orders of magnitude larger than that of dried substrates, but also provides the structural basis for trapping molecules. Even a single molecule of resonant dye can generate a large SERS signal. With a portable Raman spectrometer, the detection capability is also greatly improved for various analytes with different natures, including pesticides and drugs. This 3D hotspot matrix overcomes the long-standing limitations of SERS for the ultrasensitive characterization of various substrates and analytes and promises to transform SERS into a practical analytical technique

Plasmon-Induced Magnetic Resonance Enhanced Raman Spectroscopy

Plasmon-induced magnetic resonance has shown great potentials in optical metamaterials, chemical (bio)-sensing, and surface-enhanced spectroscopies. Here, we have theoretically and experimentally revealed (1) a correspondence of the strongest near-field response to the far-field scattering valley and (2) a significant improvement in Raman signals of probing molecules by the plasmon-induced magnetic resonance. These revelations are accomplished by designing a simple and practical metallic nanoparticle–film plasmonic system that generates magnetic resonances at visible-near-infrared frequencies. Our work may provide new insights for understanding the enhancement mechanism of various plasmon-enhanced spectroscopies and also helps further explore light-matter interactions at the nanoscale

Plasmon-Enhanced Second-Harmonic Generation Nanorulers with Ultrahigh Sensitivities

Attainment of spatial resolutions far below diffraction limits by means of optical methods constitutes a challenging task. Here, we design nonlinear nanorulers that are capable of accomplishing approximately 1 nm resolutions by utilizing the mechanism of plasmon-enhanced second-harmonic generation (PESHG). Through introducing Au@SiO₂ (core@shell) shell-isolated nanoparticles, we strive to maneuver electric-field-related gap modes such that a reliable relationship between PESHG responses and gap sizes, represented by “PESHG nanoruler equation”, can be obtained. Additionally validated by both experiments and simulations, we have transferred “hot spots” to the film-nanoparticle-gap region, ensuring that retrieved PESHG emissions nearly exclusively originate from this region and are significantly amplified. The PESHG nanoruler can be potentially developed as an ultrasensitive optical method for measuring nanoscale distances with higher spectral accuracies and signal-to-noise ratios