Continuous-Wave Raman Lasing from Metal-Linked Organic Dimer Microcrystals.

Stimulated Raman scattering offers an alternative strategy to explore continuous-wave (c.w.) organic lasers, which, however, still suffers from the limitation of inadequate Raman gain in organic material systems. Here we propose a metal-linking approach to enhance the Raman gain of organic molecules. Self-assembled microcrystals of the metal linked organic dimers exhibit large Raman gain, therefore allowing for c.w. Raman lasing. Furthermore, broadband tunable Raman lasing is achieved in the organic dimer microcrystals by adjusting excitation wavelengths. This work advances the understanding of Raman gain in organic molecules, paving a way for the design of c.w. organic lasers.

Spatially Resolved Organic Whispering-Gallery-Mode Hetero-Microrings for High-Security Photonic Barcodes.

Whispering-gallery-mode (WGM) microcavities featuring distinguishable sharp peaks in a broadband exhibit enormous advantages in the field of miniaturized photonic barcodes. However, such kind of barcodes developed hitherto are primarily based on microcavities wherein multiple gain medias were blended into a single matrix, thus resulting in the limited and indistinguishable coding elements. Here, a surface tension assisted heterogeneous assembly strategy is proposed to construct the spatially resolved WGM hetero-microrings with multiple spatial colors along its circular direction. Through precisely regulating the charge-transfer (CT) strength, full-color microrings covering the entire visible range were effectively acquired, which exhibit a series of sharp and recognizable peaks and allow for the effective construction of high-quality photonic barcodes. Notably, the spatially resolved WGM hetero-microrings with multiple coding elements were finally acquired through heterogeneous nucleation and growth controlled by the directional diffusion between the hetero-emulsion droplets, thus remarkably promoting the security strength and coding capacity of the barcodes. The results would be useful to fabricate new types of organic hierarchical hybrid WGM heterostructures for optical information recording and security labels.

Simulating the Structure of Carbon Dots via Crystalline π-Aggregated Organic Nanodots Prepared by Kinetically Trapped Self-Assembly.

This work reports the successful preparation of a new type of crystalline luminescent organic nanodot (<3.5 nm) by kinetically trapped self-assembly, which is then used as a simplified π-packing model to simulate the structure of CDs. The precise structure and J-aggregation-induced photoluminescence (PL) of the nanodots are revealed by investigating the structural relationship between the nanodots and the corresponding single crystals and their properties. Compared with the single crystals, crystalline organic nanodots show longer PL lifetime, higher PL quantum yield, and narrower PL peak, indicating that they are potential organic quantum nanodots. In addition, the efficient π-stacking environment in the corresponding single crystals can promote π-aggregation-induced PL anisotropy. This work indicates crystalline organic nanodots with precise structures to be potentially useful for understanding the structures of CDs and to be attractive potential luminescent materials.

Thermally Activated Lasing in Organic Microcrystals toward Laser Displays.

Thermally activated delayed fluorescent (TADF) materials are promising to overcome triplet-induced optical loss in the pursuit of electrically pumped organic lasers. However, population inversion is difficult to establish in these materials due to the severe suppression of triplet-to-singlet upconversion in their condensed states. In this work, we report thermally activated lasing in solution-processed coassembled microcrystals, where TADF dyes were uniformly dispersed into crystalline matrices to ensure an efficient reverse intersystem crossing (RISC). The dark-state triplet excitons harvested by the RISC were effectively converted into radiative singlet excitons, which subsequently participated in the population inversion to boost lasing with an unusual temperature dependence. The lasing wavelength was tuned over the full visible spectrum by doping various TADF laser dyes, owing to the excellent compatibility. Trichromatic TADF microlasers were precisely patterned into periodic pixelated arrays by a template-confined solution-growth method. With as-prepared TADF microlaser arrays as display panels, vivid laser displays were achieved under programmable excitation. These results offer valuable enlightenment to minimize triplet state-related energy losses toward high-performance lasers.

Topological-Distortion-Driven Amorphous Spherical Metal-Organic Frameworks for High-Quality Single-Mode Microlasers.

Metal-organic frameworks (MOFs) have recently emerged as appealing platforms to construct microlasers owing to their compelling characters combining the excellent stability of inorganic materials and processable characters of organic materials. However, MOF microstructures developed thus far are generally composed of multiple edge boundaries due to their crystalline nature, which consequently raises significant scattering losses that are detrimental to lasing performance. In this work, we propose a strategy to overcome the above drawback by designing spherically shaped MOFs microcavities. Such spherical MOF microstructures are constructed by amorphizing MOFs with a topological distortion network through introducing flexible building blocks into the growth environment. With an ultra-smooth surface and excellent circular boundaries, the acquired spherical microcavities possess a Q factor as high as ≈104 and can provide sufficient feedback for high-quality single-mode lasing oscillations. We hope that these results will pave an avenue for the construction of new types of flexible MOF-based photonic components.

Light-Emitting Metal-Organic Halide 1D and 2D Structures: Near-Unity Quantum Efficiency, Low-Loss Optical Waveguide and Highly Polarized Emission.

Organic-inorganic metal-halide materials (OIMMs) with zero-dimensional (0D) structures offer useful optical properties with a wide range of applications. However, successful examples of 0D structural OIMMs with well-defined optical performance at the micro-/nanometer scale are limited. We prepared one-dimensional (1D) (DTA)2 SbCl5 ⋅DTAC (DTAC=dodecyl trimethyl ammonium chloride) single-crystal microrods and 2D microplates with a 0D structure in which individual (SbCl5 )2- quadrangular units are completely isolated and surrounded by the organic cation DTA+ . The organic molecular unit with a long alkyl chain (C12 ) and three methyl groups enables microrod and -plate formation. The single-crystal microrods/-plates exhibit a broadband orange emission peak at 610 nm with a photoluminescence quantum yield (PLQY) of ca. 90 % and a large Stokes shift of 260 nm under photoexcitation. The broad emission originates from self-trapping excitons. Spatially resolved PL spectra confirm that these microrods exhibit an optical waveguide effect with a low loss coefficient (0.0019 dB µm-1 ) during propagation, and linear polarized photoemission with a polarization contrast (0.57).

Laterally Engineering Lanthanide-MOFs Epitaxial Heterostructures for Spatially Resolved Planar 2D Photonic Barcoding.

Metal-organic frameworks (MOFs) heterostructures with domain-controlled emissive colors have shown great potential for achieving high-throughput sensing, anti-counterfeit and information security. Here, a strategy based on steric-hindrance effect is proposed to construct lateral lanthanide-MOFs (Ln-MOFs) epitaxial heterostructures, where the channel-directed guest molecules are introduced to rebalance in-plane and out-of-plane growth rates of the Ln-MOFs microrods and eventually generate lateral MOF epitaxial heterostructures with controllable aspect ratios. A library of lateral Ln-MOFs heterostructures are acquired through a stepwise epitaxial growth procedure, from which rational modulation of each domain with specific lanthanide doping species allows for definition of photonic barcodes in a two-dimensional (2D) domain with remarkably enlarged encoding capacity. The results provide molecular-level insight into the use of modulators in governing crystallite morphology for spatially assembling multifunctional heterostructures.

Spatially Responsive Multicolor Lanthanide-MOF Heterostructures for Covert Photonic Barcodes.

Micro/nanoscale photonic barcodes based on multicolor luminescent segmented heterojunctions hold potential for applications in information security. However, such multicolor heterojunctions reported thus far are exclusively based on static luminescent signals, thus restricting their application in advanced confidential information protection. Reported here is a strategy to design responsive photonic barcodes with heterobimetallic (Tb3+ /Eu3+ ) metal-organic framework multicolor heterostructures. The spatial colors could be precisely controlled by thermally manipulating the energy-transfer process between the two lanthanides, thus achieving responsive covert photonic barcodes. Also demonstrated is that spatially resolved responsive barcodes with multi-responsive features could be created in a single heterostructure. These findings offer unique opportunities to purposely design highly integrated responsive microstructures and smart devices toward advanced anti-counterfeiting applications.

Circularly Polarized Luminescence from Achiral Single Crystals of Hybrid Manganese Halides.

[K(dibenzo-18-crown-6)]+ (KC) cations are used for cocrystallization with manganese halides, producing isostructural single crystals of organic-inorganic hybrid complexes, [K(dibenzo-18-crown-6)]2MnX4 (abbreviated (KC)2MnX4) (X = Cl, Br), which feature one-dimensional morphology and green phosphorescence with considerable photoluminescence quantum yields accompanied by excellent optical waveguide behavior with a low loss coefficient. More interestingly, (KC)2MnX4 crystallizes in the monoclinic space group Cc belonging to the achiral point group m (Cs), where the non-centrosymmetric arrangement of racemic units, with right- and left-handed rotating optical axes, endows these achiral single crystals with circularly polarized luminescence, observed for the first time.

Two-Dimensional Lanthanide Metal-Organic Framework Heterostructures for Noninvasively Photoresponsive High-Security Photonic Barcodes.

Stimuli-responsive micro/nanoscale photonic barcodes show great capacity for encryption and anticounterfeiting technologies due to multiple authentications, yet their application is commonly restricted by invasive stimuli. Herein, we report noninvasive light-stimulated high-security photonic barcodes based on spatially assembled photoresponsive two-dimensional (2D) 1,3,5-benzenetribenzoate (BTB)@Ln-MOF host-guest heterostructures. The photoluminescence (PL) spectra information on BTB@Ln-MOF heterostructures could be precisely controlled by the different wavelengths of ultraviolet (UV) light trigger. By using the PL properties and 2D heterostructures as cryptographic primitives, spatially resolved smart photonic barcodes based on both spectral and graphical coding are realized in BTB@Ln-MOF host-guest materials. These results will pave an avenue for the development of smart stimuli-responsive photonic barcodes for anticounterfeiting applications.

Does the short-selling mechanism improve energy security? Evidence from China.

Reducing carbon emissions and improving energy efficiency are essential to respond to global climate change actively. However, improving energy security under resource and environmental constraints is the key for China to achieve high-quality and sustainable development. Thus, using the panel data at the enterprises and regional levels in China from 2013 to 2020, this research develops an energy security index to study the impact of the short-selling mechanism on energy security. The results show that China's energy security is generally on the rise under the short-selling mechanism. However, it has different degrees of impact on energy security in different energy structures, supply chains, and environments. In addition, China's energy security has a regional spillover effect under the short-selling mechanism's capital pressure and supervision governance. This paper also finds that short-selling can alleviate the supply chain's bullwhip effect and risk effect. Finally, the short-selling mechanism complements the micro-influence mechanism of energy security, and short-selling positively impacts China's energy security.

Exciton Chirality Transfer Empowers Self-Triggered Spin-Polarized Amplified Spontaneous Emission from 1D-Anchoring-3D Perovskites.

Spin-polarized lasers, arising from stimulated emission of imbalanced spin populations, play a vital role in spin-optoelectronics. It is usually tackled by external spin injection, inevitably suffering from additional losses across the barriers from injection sources to gain materials. Herein, spin-polarized coherent light emission is self-triggered from the 1D-anchoring-3D perovskites, where the imbalanced populations in achiral 3D perovskites are endowed with the spin selectivity of exciton chirality (EC) underpinned by chiral 1D perovskites. Efficient transfer of EC is enabled by rapid energy transfer, thereby creating an imbalance of the spin population of excited states. Stimulated emission of such populations brings self-triggered spin-polarized amplified spontaneous emission in the composite perovskites, yielding a higher degree of polarization (DOP) than that based on optical spin injection into bare achiral 3D perovskites. Chemical diversity of composite perovskites not only enables to adjust band gap for broadband output of spin-polarized light signals but also promises to manipulate radiative decay and spin relaxation toward remarkably increased DOP. These results highlight the importance of EC transfer mechanism for spin-polarized lasing and represent a crucial step toward the development of chiral-spintronics.

The Ca2+-CaM Signaling Pathway Mediates Potassium Uptake by Regulating Reactive Oxygen Species Homeostasis in Tobacco Roots Under Low-K+ Stress.

Potassium (K+) deficiency severely threatens crop growth and productivity. Calcium (Ca2+) signaling and its sensors play a central role in the response to low-K+ stress. Calmodulin (CaM) is an important Ca2+ sensor. However, the mechanism by which Ca2+ signaling and CaM mediate the response of roots to low-K+ stress remains unclear. In this study, we found that the K+ concentration significantly decreased in both shoots and roots treated with Ca2+ channel blockers, a Ca2+ chelator, and CaM antagonists. Under low-K+ stress, reactive oxygen species (ROS) accumulated, and the activity of antioxidant enzymes, NAD kinase (NADK), and NADP phosphatase (NADPase) decreased. This indicates that antioxidant enzymes, NADK, and NADPase might be downstream target proteins in the Ca2+-CaM signaling pathway, which facilitates K+ uptake in plant roots by mediating ROS homeostasis under low-K+ stress. Moreover, the expression of NtCNGC3, NtCNGC10, K+ channel genes, and transporter genes was significantly downregulated in blocker-treated, chelator-treated, and antagonist-treated plant roots in the low K+ treatment, suggesting that the Ca2+-CaM signaling pathway may mediate K+ uptake by regulating the expression of these genes. Overall, this study shows that the Ca2+-CaM signaling pathway promotes K+ absorption by regulating ROS homeostasis and the expression of K+ uptake-related genes in plant roots under low-K+ stress.