Promoting structural distortion to enhance the crystal field strength of Mn(II) in tetrahedral bromide for near-unity yellow emission.

Two zero-dimensional hybrid manganese bromide polymorphs ((DMAPH)2MnBr4) exhibit single-crystal to single-crystal phase transformation, accompanied by an increase in MnBr4 tetrahedral bond angle variance (σ2). This structural change leads to an emission redshift due to enhanced crystal field strength, achieving yellow emission with near-unity quantum yield, which highlights its potential for solid-state lighting applications.

Relaxed stability criteria of delayed neural networks using delay-parameters-dependent slack matrices.

This note aims to reduce the conservatism of stability criteria for neural networks with time-varying delay. To this goal, on the one hand, we construct an augmented Lyapunov-Krasovskii functional (LKF), incorporating some delay-product terms that capture more information about neural states. On the other hand, when dealing with the derivative of the LKF, we introduce several parameter-dependent slack matrices into an affine integral inequality, zero equations, and the S-procedure. As a result, more relaxed stability criteria are obtained by employing the so-called Lyapunov-Krasovskii Theorem. Two numerical examples show that the proposed stability criteria are of less conservatism compared with some existing methods.

Optical activity levels of metal centers controlling multi-mode emissions in low-dimensional hybrid metal halides for anti-counterfeiting and information encryption.

In-depth insight into the electronic competition principles between inorganic units and organic ligands proves to be extremely challenging for controlling multi-mode emissions in low-dimensional hybrid metal halides (LHMHs). Herein, an efficient blue emission from organic ligand was engineered in (DppyH)2MCl4 (Dppy = diphenyl-2-pyridylphosphine, M = Zn2+, Cd2+) due to the reverse type I band alignment constructed by optically inert units with nd10 shell electrons. By contrast, the optically active [MnCl4]2- with semi-fully filled 3d5 shell electrons prompts the band alignment of type II, resulting in the narrowband green emission of Mn2+, along with an energy transfer from DppyH+ to [MnCl4]2-. Beyond that, the band alignment of (DppyH)SbCl4 is further reversed to type I due to the strong stereochemical activity of 5s2 lone-pair electrons, resulting in the triplet-state (3P1 → 1S0) self-trapped exciton (STE) emission of [SbCl4]-. The conclusion is that the electronic configurations of metal centers govern the optical activity levels of inorganic units, which in turn controls the multi-mode emissions by maneuvering the band alignments. This research provides an enlightening perspective on the multi-mode emissions with tunable photoluminescence and resulting electronic transitions of LHMHs, whose derived emitters can be employed in anti-counterfeiting and information encryption.

Photocatalyst Au@Ni-MOFs with Different Plasmonic Coverages for Improved Hydrogen Evolution from Water.

Plasmonic materials are fundamental photosensitizer materials for photocatalytic reactions. Various structures, including core-shell types, satellite types, and distribution types, have been designed and prepared for the optimization of photocatalytic reactions. However, understanding the profound enhancement mechanism of various structures is still challenging. Thus, the plasmonic coverage is considered to be an index for analyzing the influence mechanism. Here, Au@Ni-MOF core-shell flower sphere-like photocatalysts are prepared, and the size of the flower sphere can be precisely regulated by varying the amount of Au. Thus, different plasmonic coverages are realized through the tuning of spheres of different sizes. The high plasmonic coverage of catalysts can enhance visible light absorption, facilitate the generation of photogenerated electron-hole pairs, and shorten the photogenerated carrier transport distance. Moreover, the exponential relationship between the photocatalytic hydrogen production performance and the plasmonic coverage can also be used as a guide for material design. As a result, a photocatalytic hydrogen production rate of 3389 µmol·g-1·h-1 is achieved in the Au@Ni-MOF sample with high plasmonic coverage, which will advance the plasmonic application in photocatalytic reactions.

PbBeB2O5: A High-Performance Ultraviolet Nonlinear-Optical Crystal with Functional [BeB2O8]8- Group.

High-performance nonlinear-optical (NLO) crystals need to simultaneously meet multiple basic and conflicting performance requirements. Here, by using a partial chemical substitution strategy, the first noncentrosymmetric (NCS) PbBeB2O5 crystal with a BeB2O8 group was synthesized, exhibiting a two-dimensional [BeB2O5]∞ layer constructed by interconnecting BeB2O8 groups and bridged PbO4 with an active lone pair. The crystal shows a promising UV NLO functional feature, including a strong SHG effect of 3.5 × KDP (KH2PO4), large birefringence realizing phase matchability in the whole transparency region from 246 to 2500 nm, a short UV absorption edge of 246 nm, and single-crystal easy growth. Remarkably, theoretical studies reveal that the BeB2O8 group has high nonlinear activity, which could stimulate the discovery of a series of excellent NLO beryllium borates.

A 66-Nuclear All-Alkynyl Protected Peanut-Shaped Silver(I)/Copper(I) Heterometallic Nanocluster: Intermediate in Copper-Catalyzed Alkyne-Azide Cycloaddition.

Ligand-protected heterometallic nanoclusters in contrast to homo-metal counterparts show more broad applications due to the synergistic effect of hetero-metals but their controllable syntheses remain a challenge. Among heterometallic nanoclusters, monovalent Ag-Cu compounds are rarely explored due to much difference of Ag(I) and Cu(I) such as atom radius, coordination habits, and redox potential. Encouraged by copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction, comproportionation reaction of Cu(II)X2 and Cu(0) in the presence of (PhC≡CAg)n complex and molybdate generated a core-shell peanut-shaped 66-nuclear Ag(I)-Cu(I) heterometallic nanocluster, [(Mo4O16)2@Cu12Ag54(PhC≡C)50] (referred to as Ag54Cu12). The structure and composition of Ag-Cu heterometallic nanocluster are fully characterized. X-ray single crystal diffraction reveals that Ag54Cu12 has a peanut-shaped silver(I)/copper(I) heterometallic nanocage protected by fifty phenylacetylene ligands in µ3-modes and encapsulated two mutually twisted tetramolybdates. Heterometallic nanocage contains a 54-Ag-atom outer ellipsoid silver cage decorated by 12 copper inside wall. Nanosized Ag54Cu12 is a n-type narrow-band-gap semiconductor with a good photocurrent response. Preliminary experiments demonstrates that Ag54Cu12 itself and activated carbon supported Ag54Cu12/C are effective catalysts for 1,3-dipole cycloaddition between alkynes and azides at ambient conditions. The work provides not only a new synthetic route toward Ag(I)-Cu(I) nanoclusters but also an important heterometallic intermediate in CuAAC catalytic reaction.

Metavalently bonded tellurides: the essence of improved thermoelectric performance in elemental Te.

Elemental Te is important for semiconductor applications including thermoelectric energy conversion. Introducing dopants such as As, Sb, and Bi has been proven critical for improving its thermoelectric performance. However, the remarkably low solubility of these elements in Te raises questions about the mechanism with which these dopants can improve the thermoelectric properties. Indeed, these dopants overwhelmingly form precipitates rather than dissolve in the Te lattice. To distinguish the role of doping and precipitation on the properties, we have developed a correlative method to locally determine the structure-property relationship for an individual matrix or precipitate. We reveal that the conspicuous enhancement of electrical conductivity and power factor of bulk Te stems from the dopant-induced metavalently bonded telluride precipitates. These precipitates form electrically beneficial interfaces with the Te matrix. A quantum-mechanical-derived map uncovers more candidates for advancing Te thermoelectrics. This unconventional doping scenario adds another recipe to the design options for thermoelectrics and opens interesting pathways for microstructure design.

Visible-light-promoted regioselective hydrocarboxylation of allenes with formate salt and CO2.

Visible-light-promoted hydrocarboxylation of allenes with formate salt and CO2 was developed for the first time using commercially available [Ir(ppy)2(dtbbpy)]PF6 as a photocatalyst. This strategy provides an efficient and practical method to access ß,γ-unsaturated linear carboxylic acids in moderate yields with complete regioselectivity.

Cocrystallization-driven Formation of fcc-based Ag110 Nanocluster with Chinese Triple Luban Lock Shape.

Luban locks with mortise and tenon structure have structural diversity and architectural stability, and it is extremely challenging to synthesize Luban lock-like structures at the molecular level. In this work, we report the cocrystallization of two structurally related atom-precise fcc silver nanoclusters Ag110 (SPhF)48 (PPh3 )12 (Ag110 ) and Ag14 (µ6 -S)(SPhF)12 (PPh3 )8 (Ag14 ). It is worth noting that the Ag110 cluster is the first compound to simulate the complex Luban lock structure at the molecular level. Meanwhile, Ag110 is the largest known fcc-based silver nanocluster, so far, there is no precedent for fcc silver nanocluster with more than 100 silver atoms. DFT calculations show that Ag110 is a 58-electron superatom with an electronically closed shell1S2 1P6 1D10 2S2 1F14 2P6 1G18 . Ag110 ⋅Ag14 can rapidly catalyze the reduction of 4-nitrophenol within 4 minutes. In addition, Ag110 presents clear structural evidence to reveal the critical size and mechanism of the transformation of metal core from fcc stacking to quasi-spherical superatom. This research work provides an important structural model for studying the nucleation mechanism and structural assembly of silver nanoclusters.

Surface defect-engineered Fe doping in layered Co-based complex as highly efficient bifunctional electrocatalysts for overall water splitting.

The electrocatalytic splitting of water to produce hydrogen is regarded as an efficient and promising strategy but is limited by its large overpotential; thus, a highly efficient electrocatalyst is urgently needed. Mixed metal doping is an important strategy in defect engineering because the heteroatoms can change the intrinsic structure to form defects by affecting the atomic coordination mode and adjusting the electronic structure, which is often accompanied by morphological changes. Herein, two-dimensional layered bimetallic Co-pydc containing axially coordinated water molecules was selected by producing surface defects through Fe doping in Co centers as bifunctional electrocatalysts for OER and HER. The optimized Co0.59Fe0.41-pydc possesses outstanding OER performance with the lowest overpotential of 262 mV to reach j = 10 mA cm-2, and Co0.75Fe0.25-pydc possesses superior HER performance with the lowest overpotential of 96 mV at j = 10 mA cm-2. Furthermore, the overall water splitting device assembled with Co0.59Fe0.41-pydc@NF//Co0.59Fe0.41-pydc@NF affords a current density of 10 mA cm-2 at only 1.687 V. This work emphasizes the surface defects formed by tuning the electronic structure of metal centres accompanied with morphological changes of bimetallic dopants for efficient overall water splitting.

Stereochemically Active Lone-Pair Containing Metal Substitution in Polar Axis toward a Giant Phase-Matchable Optical Nonlinear Silicate Crystal Li3(OH)PbSiO4.

Atoms in special lattice sites can play a crucial role in realizing materials properties, which is long pursued but difficult to control. Herein, by adopting a stereochemically active lone-pair-containing metal substitution strategy, a nonlinear-optical (NLO) silicate crystal Li3(OH)PbSiO4 was successfully synthesized, featuring [PbSiO4]∞ layers with the perfect orientation of the stereochemically active lone-pair Pb(II) cation in the polar-axis lattice. Li3(OH)PbSiO4 overcomes the long-standing problem of silicates, that is, poor nonlinear properties because it exhibits both the largest birefringence of 0.082 and the largest phase-matchable second-harmonic-generation (SHG) efficiency of 21 × KDP among the known silicates. The successful polar-axis lattice substitution could offer a new direction for realizing the rational control of materials structures and properties.

Tuning Binding Strength of Multiple Intermediates towards Efficient pH-universal Electrocatalytic Hydrogen Evolution by Mo8 O26 -NbNx Oy Heterocatalysts.

Developing efficient and robust hydrogen evolution reaction (HER) catalysts for scalable and sustainable hydrogen production through electrochemical water splitting is strategic and challenging. Herein, heterogeneous Mo8 O26 -NbNx Oy supported on N-doped graphene (defined as Mo8 O26 -NbNx Oy /NG) is synthesized by controllable hydrothermal reaction and nitridation process. The O-exposed Mo8 O26 clusters covalently confined on NbNx Oy nanodomains provide a distinctive interface configuration and appropriate electronic structure, where fully exposed multiple active sites give excellent HER performance beyond commercial Pt/C catalyst in pH-universal electrolytes. Theoretical studies reveal that the Mo8 O26 -NbNx Oy interface with electronic reconstruction affords near-optimal hydrogen adsorption energy and enhanced initial H2 O adsorption. Furthermore, the terminal O atoms in Mo8 O26 clusters cooperate with Nb atoms to promote the initial H2 O adsorption, and subsequently reduce the H2 O dissociation energy, accelerating the entire HER kinetics.

Photochemical Synthesis of Atomically Precise Ag Nanoclusters.

Photochemical methods are effective for controllable synthesis of silver nanoparticles with specific sizes and shapes. Whether they are capable of fabricating Ag nanoclusters (NCs) with atomic precision is yet to be proved. In this work, we synthesize an atomically precise Ag NC, [Ag25(4-MePhC≡C)20(Dpppe)3](SbF6)3 (Ag25), via a process mediated by visible light. Its total structure is determined by X-ray crystallography. The investigation of the mechanism reveals that the formation of Ag25 is triggered by a photoinduced electron-transfer (PET) process. An electron of certain amines is excited by light with wavelength shorter than 455 nm and transferred to Ag+. The amine is oxidized to the corresponding amine N-oxide. Such a PET process is supported by experimental and density functional theory studies. To expand the application scope of the photochemical method, another three NCs, [Ag19(4-tBuPhC≡C)14(Dpppe)3](SbF6)3 (Ag19), [Ag32(4-tBuPhC≡C)22(Dppp)4](SbF6)3 (Ag32), and bimetallic [Ag22Au3(4-tBuPhC≡C)20(Dpppe)3](SbF6)3 (Ag22Au3), are produced by replacing certain ingredients. Furthermore, since the formation of Ag19 can be regarded as a photochromatic process, a facile amine visual detection method is also presented based on this mechanism.

Selective Photochromic Response to Low-Dose X-ray Radiation Detection in One-Dimensional Cadmium-Viologen Complexes.

Photochromic viologen-based materials have emerged as one of the most promising candidates for the development of X-ray light detection applications, including medical diagnosis and treatment, environmental radiation inspection, and industrial crack detection. However, the design and construction of low-dose X-ray-sensitive complexes remains an immense challenge, especially for the in-depth dissection of their response mechanisms. Herein, by using N,N'-4,4'-bipyridiniodipropionate (CV) as functional sensitive structural units and cadmium as heavy atoms, two cadmium-viologen complexes with one-dimensional chained structures, namely, [Cd2Cl4(CV)(H2O)2]n (1) and [CdBr2(CV)]n (2), have been constructed, which exhibit a remarkable and selective photochromic response to low-dose X-ray radiation detection. Compound 1 is visually sensitive to both X-ray and UV light due to the more accessible photoinduced electron transfer (ET) pathways, while compound 2 only shows a slight color-changing process in response to UV light, in conformity with UV-vis absorbance analyses and kinetic studies. Surprisingly, compound 2 has longer ET pathways than 1, but not in response to high-energy X-ray light, seeming to contradict the previous phenomena. On further analysis, the key point in achieving X-ray-sensitive behavior should be a good balance among the electron donor-acceptor distance, intermolecular interaction, and X-ray absorbing capacity, as verified by density functional theory (DFT) and X-ray absorption strength calculations, X-ray photoelectron spectra, electron paramagnetic resonance measurements, and independent gradient model analysis. In particular, compound 1 is unprecedentedly sensitive to soft X-ray radiation, accompanied by an X-ray detection limit of as low as 2.91 Gy. These findings push forward the further development of low-dose X-ray sensing materials.

Entropy-Driven Ultrafast Ion Conduction Via Confining Organic Plastic Crystals in Ordered Nanochannels of Covalent Organic Frameworks.

Low conductivity over a wide temperature region due to ultra-slow ion migration dynamics is a key issue in the field of solid-state electrolytes (SSE), which needs to be solved and improved. Covalent organic frameworks (COFs), a rapidly growing class of porous crystalline materials, emerge as a new research hotspot in the field of SSEs. This is due to their homogeneously dispersed sites and well-defined pathways for ion diffusion, demonstrating great advantages over conventional non-porous solids. Herein, a composite solid electrolyte by confining organic ionic plastic crystal (OIPC) in the 1D ordered nanochannels of COFs as the host matrix for solid-state lithium-ion conduction, is reported. Due to the loss of coupling between PBu4 + cations and TFSI- anions, the cation-anion interaction is weakened; and thus, the lithium-ion transportation is facilitated. As a result, the COF-confining OIPC SSEs show ultra-high lithium-ion conductivity of 0.048 S cm-1 at 30 °C and 0.021 S cm-1 at the extremely low temperature of -30 °C. The dynamic origin of this fast ion conduction is characterized by differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and variable temperature solid-state nuclear magnetic resonance (NMR) spectroscopy.

Recoil attenuation for deepwater drilling riser systems via delayed H∞ control.

This paper deals with the recoil suppression problem of a deepwater drilling riser system via active H∞ control using both current and delayed states. First, based on the three degrees of freedom spring-mass-damping model of the riser system, an incremental dynamic equation of the system subject to the platform heave motion and the friction force induced by drilling discharge mud and seawater is established. Then, to reject recoil movements of the riser, a delayed state feedback H∞ controller with delayed states as well as current states is designed. The existence conditions and the design method of the delayed H∞ recoil controllers are presented. Third, the effects of the introduced time-delays on the recoil control of the riser are analyzed, and the design of optimal artificial time-delays is formulated as the minimum value problem of a series of quintic algebraic polynomials, which are related to the weights of average response amplitudes, steady-state errors, and the control force. Lastly, simulation results are provided to demonstrate the effectiveness of delay-free and delayed H∞ recoil control schemes for the riser. It is shown that (i) under the delayed H∞ controllers, the recoil responses of the riser can be controlled significantly; (ii) the decay rate of the recoil response under the delay-free H∞ controller is slightly faster than the one under the delayed H∞ controllers. However, the former requires more control cost than the latter; (iii) compared with the delayed H∞ controller with the existing linear quadratic optimal controller, the control cost by the former is larger than that by the latter. However, the steady-state errors of the riser under the latter are slightly smaller than that under the former; (iv) the introduced time-delays with proper size play positive role of suppressing recoil response of the system, and the corresponding delayed H∞ controller series provide more options for recoil control of the riser.

Delay-Variation-Dependent Criteria on Extended Dissipativity for Discrete-Time Neural Networks With Time-Varying Delay.

This article is concerned with the extended dissipativity of discrete-time neural networks (NNs) with time-varying delay. First, the necessary and sufficient condition on matrix-valued polynomial inequalities reported recently is extended to a general case, where the variable of the polynomial does not need to start from zero. Second, a novel Lyapunov functional with a delay-dependent Lyapunov matrix is constructed by taking into consideration more information on nonlinear activation functions. By employing the Lyapunov functional method, a novel delay and its variation-dependent criterion are obtained to investigate the effects of the time-varying delay and its variation rate on several performances, such as H∞ performance, passivity, and l2-l∞ performance, of a delayed discrete-time NN in a unified framework. Finally, a numerical example is given to show that the proposed criterion outperforms some existing ones.

Stability Analysis for Delayed Neural Networks via a Generalized Reciprocally Convex Inequality.

This article deals with the stability of neural networks (NNs) with time-varying delay. First, a generalized reciprocally convex inequality (RCI) is presented, providing a tight bound for reciprocally convex combinations. This inequality includes some existing ones as special case. Second, in order to cater for the use of the generalized RCI, a novel Lyapunov-Krasovskii functional (LKF) is constructed, which includes a generalized delay-product term. Third, based on the generalized RCI and the novel LKF, several stability criteria for the delayed NNs under study are put forward. Finally, two numerical examples are given to illustrate the effectiveness and advantages of the proposed stability criteria.

Water induced ultrathin Mo2C nanosheets with high-density grain boundaries for enhanced hydrogen evolution.

Grain boundary controlling is an effective approach for manipulating the electronic structure of electrocatalysts to improve their hydrogen evolution reaction performance. However, probing the direct effect of grain boundaries as highly active catalytic hot spots is very challenging. Herein, we demonstrate a general water-assisted carbothermal reaction strategy for the construction of ultrathin Mo2C nanosheets with high-density grain boundaries supported on N-doped graphene. The polycrystalline Mo2C nanosheets are connected with N-doped graphene through Mo-C bonds, which affords an ultra-high density of active sites, giving excellent hydrogen evolution activity and superior electrocatalytic stability. Theoretical calculations reveal that the dz2 orbital energy level of Mo atoms is controlled by the MoC3 pyramid configuration, which plays a vital role in governing the hydrogen evolution activity. The dz2 orbital energy level of metal atoms exhibits an intrinsic relationship with the catalyst activity and is regarded as a descriptor for predicting the hydrogen evolution activity.

Blue Light-Excitable Broadband Yellow Emission in a Zero-Dimensional Hybrid Bismuth Halide with Type-II Band Alignment.

Zero-dimensional (0D) organic-inorganic hybrid metal halides have captured broad interest in the lighting and display fields because of their unique electronic structures and splendid broadband emission properties. However, the blue light-excitable broadband yellow emissions have been rarely reported in 0D hybrid metal halides. Here, we design a new 0D bismuth hybrid, (4cmpyH)2BiCl5 (1, 4cmpy = 4-(chloromethyl)pyridine), featuring isolated edge-sharing bioctahedral [Bi2Cl10]4- dimers surrounded by rigid, conjugated, and luminescent organic [4cmpyH]+ cations. This material is able to show intrinsic broadband yellow emissions under blue light (468 nm) excitation with a long lifetime of 22.33 µs and a photoluminescence (PL) quantum yield of 5.56%. Solid-state UV-vis spectroscopy studies prove that introducing organic π-conjugated groups into hybrid systems leads to absorption in the visible light region, in favor of photoexcitation by visible light. By comparing the PL data of 1 and the organic template at room temperature and measuring variable-temperature PL spectra of 1, the blue light-excited broadband emission of 1 can be attributed to the synergistic emissions of intramolecular π → π* and n → π* transitions in the organic cations and triple self-trapped exciton (STE) states centralized at the highly distorted Bi-Cl lattices. Moreover, density functional theory calculations reveal a type-II band alignment in 1 with an indirect band gap of 2.64 eV, which is together determined by organic cations and inorganic bioctahedral units. To the best of our knowledge, our work represents the first report on the blue light-excitable STE emission in 0D Bi-based metal halides, which will largely promote the rapid development of novel high-performance yellow light-emitting materials.