Regulating Spin Density using TEMPOL Molecules for Enhanced CO2-to-Ethylene Conversion by HKUST-1 Framework Derived Electrocatalysts.

The selectivity of multicarbon products in the CO2 reduction reaction (CO2RR) depends on the spin alignment of neighboring active sites, which requires a spin catalyst that facilitates electron transfer with antiparallel spins for enhanced C-C coupling. Here, we design a radical-contained spin catalyst (TEMPOL@HKUST-1) to enhance CO2-to-ethylene conversion, in which spin-disordered (SDO) and spin-ordered (SO) phases co-exist to construct an asymmetric spin configuration of neighboring active sites. The replacement of axially coordinated H2O molecules with TEMPOL radicals introduces spin-spin interactions among the Cu(II) centers to form localized SO phases within the original H2O-mediated SDO phases. Therefore, TEMPOL@HKUST-1 derived catalyst exhibited an approximately two-fold enhancement in ethylene selectivity during the CO2RR at -1.8 V versus Ag/AgCl compared to pristine HKUST-1. In situ ATR-SEIRAS spectra indicate that the spin configuration at asymmetric SO/SDO sites significantly reduces the kinetic barrier for *CO intermediate dimerization toward the ethylene product. The performance of the spin catalyst is further improved by spin alignment under a magnetic field, resulting in a maximum ethylene selectivity of more than 50 %. The exploration of the spin-polarized kinetics of the CO2RR provides a promising path for the development of novel spin electrocatalysts with superior performance.

Crystal-Liquid-Glass Transition and Near-Unity Photoluminescence Quantum Yield in Low Melting Point Hybrid Metal Halides.

Hybrid metal halides (HMHs) are a class of materials that combine extraordinary photophysical properties and excellent processability. Their chemical variability allows for the solid-liquid transition toward melt-processable HMHs. Herein, we report the design and synthesis of zero-dimensional HMHs [M(DMSO)6][SbCl6], where the isolated octahedra of [M(DMSO)6]3+ and [SbCl6]3- are alternatively aligned in the crystal structure. The luminescent center of [SbCl6]3- enables the photogeneration of self-trapped excitons, resulting in broadband photoluminescence with a large Stokes shift and a nearly 100% quantum yield. Meanwhile, the release of DMSO ligands from [M(DMSO)6]3+ is controlled by the M-O coordination and thus a low melting point of ∼90 °C is achieved for HMHs. Interestingly, the glass phase is obtained by melt quenching, with a sharp change in photoluminescence colors compared to the crystal phase of melt-processable HMHs. The robust crystal-liquid-glass transition opens a new avenue to tailoring structural disorder and optoelectronic performance in organic-inorganic materials.

A Paramagnetic Compass Based on Lanthanide Metal-Organic Framework.

Macroscopic compass-like magnetic alignment at low magnetic fields is natural for ferromagnetic materials but is seldomly observed in paramagnetic materials. Herein, we report a "paramagnetic compass" that magnetically aligns under ∼mT fields based on the single-crystalline framework constructed by lanthanide ions and organic ligands (Ln-MOF). The magnetic alignment is attributed to the Ln-MOF's strong macroscopic anisotropy, where the highly-ordered structure allows the Ln-ions' molecular anisotropy to be summed according to the crystal symmetry. In tetragonal Ln-MOFs, the alignment is either parallel or perpendicular to the field depending on the easiest axis of the molecular anisotropy. Reversible switching between the two alignments is realized upon the removal and re-adsorption of solvent molecules filled in the framework. When the crystal symmetry is lowered in monoclinic Ln-MOFs, the alignments become even inclined (47°-66°) to the field. These fascinating properties of Ln-MOFs would encourage further explorations of framework materials containing paramagnetic centers.

Optically Triggering and Monitoring Single-Cell-Level Metabolism Using Ormosil-Decorated Ultrathin Fibers.

The integration of biological components and artificial devices requires a bio-machine interface that can simultaneously trigger and monitor the activities in biosystems. Herein, we use an organically modified silicate (ormosil) composite coating containing a light-responsive nanocapsule and a fluorescent bioprobe for reactive oxygen species (ROS) to decorate ultrathin optical fibers, namely, ormosil-decorated ultrathin fibers (OD-UFs), and demonstrate that these OD-UFs can optically trigger and monitor the intracellular metabolism activities in living cells. The sizes and shapes of UF tips were finely controlled to match the dimension and mechanical properties of living cells. The increased elasticity of the ormosil coating of OD-UFs reduces possible mechanical damage during the cell membrane penetration. The light-responsive nanocapsule was physically absorbed on the surface of the ormosil coating and could release a stimulant to trigger the metabolism activities in cells upon the guided laser through OD-UFs. The fluorescent bioprobe was covalently linked with the ormosil matrix for monitoring the intracellular ROS generation, which was verified by the in vitro experiments on the microdroplets of a hydrogen peroxide solution. Finally, we found that the living cells could maintain most of their viability after being inserted with OD-UFs, and the intracellular metabolism activities were successfully triggered and monitored at the single-cell level. The OD-UF provides a new platform for the investigation of intracellular behaviors for drug stimulations and represents a new proof of concept for a bio-machine interface based on the optical and chemical activities of organic functional molecules.

Controllable synthesis of nickel bicarbonate nanocrystals with high homogeneity for a high-performance supercapacitor.

The electrochemical performance of supercapacitors might be associated with the homogeneous structure of the electrode materials. However, the relationship between the degree of uniformity for the electrode materials and the electrochemical performance of the supercapacitor is not clear. Herein, we synthesize two types of nickel bicarbonate nanocrystals with different degrees of uniformity to investigate this relationship. As the electroactive material, the nickel bicarbonate nanocrystals with a homogeneous structure could provide a larger space and offer more exposed atoms for the electrochemical reaction than the nanocrystals with a heterogeneous structure. The homogeneous nickel bicarbonate nanocrystals exhibit better electrochemical performance and show excellent specific capacitance (1596 F g-1 at 2 A g-1 and 1260 F g-1 at 30 A g-1), which is approximately twice that of the heterogeneous nickel bicarbonate nanocrystals. The cycling stability for the homogeneity (∼80%) is higher than the inhomogeneity (∼61%) at a high current density of 5 A g-1.

Stepwise Charge/Energy Transfer in MR-TADF Molecule-Doped Exciplex for Ultralong Persistent Luminescence Activated with Visible Light.

Organic long-persistent luminescence (OLPL), which relies on energy storage for delayed light emission by the charge separation state, has attracted intense attention in various optical applications. However, charge separation (CS) is efficient only under ultraviolet excitation in most OLPL systems because it requires a driving force from the large energy difference between the local excited (LE) and charge transfer (CT) states. In this study, a multiresonance thermally activated delayed fluorescence (MR-TADF) molecule is incorporated into an exciplex system to achieve efficient OLPL in a composite material activated by visible light via a stepwise charge/energy transfer process. The enhanced absorption of the composite material facilitated a tenfold increase in the duration of the OLPL, which can last for several hours under visible light excitation. The excited state of the MR-TADF molecule tends to charge transfer to the acceptor, followed by energy transfer to the exciplex, which benefits from the small difference between the LE and CT states owing to the inherent CS characteristics of the opposing resonance effect. Afterglow displays of these composite materials are fabricated to demonstrate their considerable potential in encryption patterns and emergency lights, which take advantage of their excellent processability, visible light activation, and tunable luminescence properties.

Magnetic Switching of Second-Harmonic Generation from Single Cerium-Based Coordination Polymer Microcrystals.

Conventional access and modulation of second-harmonic generation (SHG) require precise control of crystal orientation, which faces great mechanical challenges in the case of micro/nanocrystals. Here, we demonstrate the magnetic-field-tunable SHG performance of lanthanide coordination polymer (Ce-BTC CP) microcrystals through field-aligned orientations. The coordination of Ce ions and organic ligands constructs a noncentrosymmetric structure, which not only contributes to a favorable powder SHG efficiency 3.2 times larger than that of the benchmark KH2PO4 (KDP) but also endows the microcrystals with strong magnetic anisotropy. The SHG efficiency (∼0 to 10 × KDP) depends on the orientation of the crystallographic c-axis, whereas magnetic anisotropy always aligns the c-axis with the magnetic field at a specific angle. Accordingly, the SHG can be magnetically switched by field-induced alignments. The adsorption of dyes by Ce-BTC CPs further facilitates the magnetic switching of multicolor fluorescence that can be excited by the SHG. Our work provides a new pathway for achieving SHG modulation at the microscopic level.

Giant magneto-photoluminescence at ultralow field in organic microcrystal arrays for on-chip optical magnetometer.

Optical detection of magnetic field is appealing for integrated photonics; however, the light-matter interaction is usually weak at low field. Here we observe that the photoluminescence (PL) decreases by > 40% at 10 mT in rubrene microcrystals (RMCs) prepared by a capillary-bridge assembly method. The giant magneto-PL (MPL) relies on the singlet-triplet conversion involving triplet-triplet pairs, through the processes of singlet fission (SF) and triplet fusion (TF) during radiative decay. Importantly, the size of RMCs is critical for maximizing MPL as it influences on the photophysical processes of spin state conversion. The SF/TF process is quantified by measuring the prompt/delayed PL with time-resolved spectroscopies, which shows that the geminate SF/TF associated with triplet-triplet pairs are responsible for the giant MPL. Furthermore, the RMC-based magnetometer is constructed on an optical chip, which takes advantages of remarkable low-field sensitivity over a broad range of frequencies, representing a prototype of emerging opto-spintronic molecular devices.

Magnetically controlled assembly: a new approach to organic integrated photonics.

Hierarchical self-assembly of organic molecules or assemblies is of great importance for organic photonics to move from fundamental research to integrated and practical applications. Magnetic fields with the advantages of high controllability, non-contact manipulation, and instantaneous response have emerged as an elegant way to prepare organic hierarchical nanostructures. In this perspective, we outline the development history of organic photonic materials and highlight the importance of organic hierarchical nanostructures for a wide range of applications, including microlasers, optical displays, information encoding, sensing, and beyond. Then, we will discuss recent advances in magnetically controlled assembly for creating organic hierarchical nanostructures, with a particular focus on their potential for enabling the development of integrated photonic devices with unprecedented functionality and performance. Finally, we present several perspectives on the further development of magnetically controlled assembly strategies from the perspective of performance optimization and functional design of organic integrated photonics.

Magnetic Domain Confined Printing of Programmable Organic Microcrystal Assemblies for Information Encryption.

Large-scale assembly of organic micro/nanocrystals into well-defined patterns with programmable structures is essential for applications such as information encryption at both high data density and high security level. Here, a magnetic-field-assisted approach that produces programmable assemblies of organic microcrystals with various shapes and orientations, using the magnetic domains of the underlying ferromagnetic metal microarrays as the printing templates, is developed. The diamagnetic microcrystals tend to aggregate in the regions of minimal field strength, and thus their assembly behavior is precisely controlled by the local field distribution on top of magnetic domains on substrate. The dynamic assembly process of microcrystal assemblies can be programmed upon the sequence of applied field, and their shape changes are ≈100% reproducible on a large scale (>20 000 sites over 1 cm2 ). These features of magnetically programmable assemblies are ideally suited for information encryption, for which the encryption-decryption-erasing of multilevel information from a QR-code pattern based on the microcrystal assemblies under magnetic field is demonstrated.

Magnetic-Field-Driven Reconfigurable Microsphere Arrays for Laser Display Pixels.

Reconfigurable microlaser arrays are essential to the construction of display panels where the individual pixel should be highly tunable in resonance mode, optical polarization, and lasing wavelength upon external control signals. Here we demonstrate a facile yet reliable approach to fabrication of organic microlaser pixels, in which the assembly of microsphere arrays on each pixel is controlled according to the near-field magnetostatic confinement. The geometrical configuration of diamagnetic microspheres could be readily modulated with the near-field potential traps by using the external field to alternate the saturation magnetization of the underneath micromagnet. The motion of microspheres can be modulated among several states upon applied field, and the reconfigurable microsphere array is thus achieved with high spatial precision and rapid temporal response. Moreover, both isolated and coupled spheres serve as low-threshold microlasers with tunable optical resonance modes, whereas the switching between the vertical and horizontal alignments of coupled spheres manipulates the polarization of lasing outputs. By repeating the magnetostatic confinement on the same substrate, the full-color laser display pixels with magnetically tunable color expression capability are successfully achieved.

Nonconfinement growth of edge-curved molecular crystals for self-focused microlasers.

Synthesis of single-crystalline micro/nanostructures with curved shapes is essential for developing extraordinary types of optoelectronic devices. Here, we use the strategy of liquid-phase nonconfinement growth to controllably synthesize edge-curved molecular microcrystals on a large scale. By varying the molecular substituents on linear organic conjugated molecules, it is found that the steric hindrance effect could minimize the intrinsic anisotropy of molecular stacking, allowing for the exposure of high-index crystal planes. The growth rate of high-index crystal planes can be further regulated by increasing the molecular supersaturation, which is conducive to the cogrowth of these crystal planes to form continuously curved-shape microcrystals. Assisted by nonrotationally symmetric geometry and optically smooth curvature, edge-curved microcrystals can support low-threshold lasing, and self-focusing directional emission. These results contribute to gaining an insightful understanding of the design and growth of functional molecular crystals and promoting the applications of organic active materials in integrated photonic devices and circuits.

Magnetically modulated photochemical reaction pathways in anthraquinone molecules and aggregates.

The chemical reactions involving excited-state radical pairs (RPs) of parallel/anti-parallel spin configurations are sensitive to magnetic field, leading to the possibilities of magnetically controlled synthesis of chemical compounds. Here we show that the reaction of anthraquinone (AQ) in sodium dodecyl sulfate (SDS) micellar solution under UV excitation is significantly influenced by applying external field. The steady state and time-resolved spectroscopies reveal that the reaction intermediate (pairs of AQH-SDS radicals) can undergo two distinct pathways depending on whether it is spin singlet or triplet, and the field is beneficial to the conversion between spin configurations of RPs. The applied field not only affects the reaction rate constant but also changes the final products. Besides, the aggregation of AQ molecules would change the population of singlets and triplets and thus enhance magnetic field effect. This work represents a promising way of controlling chemical reaction and improving reaction selectivity via magnetic field methods.

Epitaxial growth of dual-color-emitting organic heterostructures via binary solvent synergism driven sequential crystallization.

The controlled construction of organic heterostructured architectures derived from molecules with similar nucleation thresholds and concentrations has been rare and remains a great challenge. Herein, we report a sequential epitaxial growth to synthesize dual-color-emitting organic heterostructures with 9,10-bis(phenylethynyl)anthracene (BPEA) microwire trunks and tris-(8-hydroxyquinoline)aluminium (Alq3) microstructure branches by an anti-solvent induced sequential crystallization strategy. During the epitaxial growth process, the hydrogen-bonding interactions of the anti-solvent and solvent cause a large change in the solubility and crystallization rate of BPEA and Alq3 molecules in the mixed system, which facilitates sequential crystallization of organic molecule pairs with similar nucleation thresholds and concentrations into desired heterostructures by manipulating the synergism of anti-solvents and solvents. The Förster resonant energy transfer process in heterostructures could be modulated by varying the structure of heterostructures, such as the shape, amount and angles of the branches. The present synthesis strategy provides a unique insight into the detailed formation mechanism of complex organic heterostructures, further guiding the construction of more functional heterostructure materials.

Homoleptic cyclometalated iridium(III) complex nanowires electrogenerated chemiluminescence sensors for high-performance discrimination of proline enantiomers based on the difference of electron-transfer capability.

Chiral molecules can generally exhibit different physiological and biological activities, thus triggering wide interest in chiral discrimination. Herein, we demonstrate a sensitive homoleptic cyclometalated iridium(III) complexes nanowires (Ir(piq)3 NWs) electrogenerated chemiluminescence (ECL) sensor for high-performance discrimination of chiral molecules based on the difference in electron-transfer ability between different radicals. The developed Ir(piq)3 NWs/ITO sensor exhibits high ECL signal and satisfying stability without the presence of co-reactant based on hot electron-induced ECL, which would spur its further application in detecting proline enantiomers. Obvious difference on the ECL intensity towards L-Pro and D-Pro is observed under the presence of high concentration of proline enantiomers, which attributes to the different electron-transfer capability between Ir+(piq)3 and L-pro•/D-pro•. In order to attain high-performance discrimination, we construct the Ir(piq)3 NWs/TPrA sensor to achieve chiral discrimination for trace amounts of proline enantiomers (1.0 × 10-9 M), which attributes to the strong molecular interactions enhanced by introduction of active radical TPrA•.

Solvent engineering for high conversion yields of layered raw materials into large-scale freestanding hybrid perovskite nanowires.

Hybrid organic-inorganic perovskite nanowires have received considerable attention for applications in optoelectronic fields; however, practical implementation of perovskite nanowires into optoelectronic devices is often hindered by low product yields, scaled-up synthesis, or overall lack of synthetic control. Herein, we report novel insights into large-scale freestanding lead halide perovskite nanowires using a series of solvent effects. A facile pathway for converting layered raw materials to nanowires with high conversion yields can facilitate the large-scale applications of nanowires, which could help us understand the unique aspects of the formation chemistry of the materials. We introduced a two-step process to obtain perovskite nanowires without an impurity phase that first involves the formation of Pb-containing nanowires with the poor solvent drip method. Subsequently, the as-prepared Pb-containing precursors can be used as morphology templates for converting completely into perovskite nanowires with high conversion yields of 83% through a series of solvent effects, such as solvent-driven, solvent-removing, solvent-exchange and solvent-growth. The synthetic strategy was demonstrated to be applicable for other perovskite-based materials, which can offer a comprehensive understanding of the formation mechanism of perovskite-based materials.

Surface tension driven aggregation of organic nanowires via lab in a droplet.

Directing the architecture of complex organic nanostructures is desirable and still remains a challenge in areas of materials science due to their structure-dependent collective optoelectronic properties. Herein, we demonstrate a simple and versatile solution strategy that allows surface tension to drive low-dimensional nanostructures to aggregate into complex structures via a lab in a droplet technique. By selecting a suitable combination of a solvent and an anti-solvent with controllable surface tension difference, the droplets can be automatically cracked into micro-droplets, which provides an aggregation force directed toward the centre of the droplet to drive the low-dimensional building blocks to form the special aggregations during the self-assembly process. This synthetic strategy has been shown to be universal for organic materials, which is beneficial for further optimizing the optoelectronic properties. These results contribute to gaining an insightful understanding on the detailed growth mechanism of complex organic nanostructures and greatly promoting the development of organic nanophotonics.

Simultaneous structure and luminescence property control of barium carbonate nanocrystals through small amount of lanthanide doping.

Rare earth doping has been widely applied in many functional nanomaterials with desirable properties and functions, which would have a significant effect on the growth process of the materials. However, the controlling strategy is limited into high concentration of lanthanide doping, which produces concentration quenching of the lanthanide ion luminescence with an increase in the Ln3+ concentration, resulting in lowering the fluorescence quantum yield of lanthanide ion. Herein, for the first time, we demonstrate simultaneous control of the structures and luminescence properties of BaCO3 nanocrystals via a small amount of Tb3+ doping strategy. In fact, Tb3+ would partially occupy Ba2+ sites, resulting in the changes to the structures of the BaCO3 nanocrystals, which is primarily determined by charge modulation, including the contributions from the surfaces of crystal nuclei and building blocks. These structurally modified nanocrystals exhibit tunable luminescence properties, thus emerging as potential candidates for photonic devices such as light-emitting diodes and color displays.