Realizing Color Transitions for Three Copper (I) Cluster Organic-Inorganic Hybrid Materials by Adjusting Reaction Conditions.

Copper iodide organic-inorganic hybrid materials have been favored by many researchers in the field of solid-state lighting (SSL) due to their structural diversity and optical adjustability. In this paper, three isomeric copper iodide cluster hybrid materials, Cu4I6(L)2(1), Cu5I4.5Cl2.5(L)2(2) and Cu5I7(L)2) (3) (L=1-(4-methylpyrimidin-2-yl)-1,4-diazabicyclo[2.2.2]octan-1-ium), were achieved by adjusting the reaction conditions. The crystal color transit from green, yellow to orange and the internal quantum yield (IQY) increase from 57 %-88 %. All three complexes have good thermal stability, good solution processability, and high quantum yield. And origin and mechanism of luminescence of complexes were further studied. This study can provide ideas and theoretical basis for the regulation of cuprous iodide cluster luminescent materials.

Facile Control of Ferroelectricity Driven by Ingenious Interaction Engineering.

Construction of ferroelectric and optimization of macroscopic polarization has attracted tremendous attention for next generation light weight and flexible devices, which brings fundamental vitality for molecular ferroelectrics. However, effective molecular tailoring toward cations makes ferroelectric synthesis and modification relatively elaborate. Here, the study proposes a facile method to realize triggering and optimization of ferroelectricity. The experimental and theoretical investigation reveals that orientation and alignment of polar cations, dominated factors in molecular ferroelectrics, can be controlled by easily processed anionic modification. In one respect, ferroelectricity is induced by strengthened intermolecular interaction. Moreover, ≈50% of microscopic polarization enhancement (from 8.07 to 11.68 µC cm-2 ) and doubling of equivalent polarization direction (from 4 to 8) are realized in resultant ferroelectric FEtQ2ZnBrI3 (FEQZBI, FEtQ = N-fluoroethyl-quinuclidine). The work offers a totally novel platform for control of ferroelectricity in organic-inorganic hybrid ferroelectrics and a deep insight of structure-property correlations.

Precise Design of Molecular Ferroelectrics with High TC and Tunable Band Gap by Molecular Modification.

Molecular ferroelectric materials are widely applied in piezoelectric converters, non-volatile memorizers, and photovoltaic devices due to their advantages of adjustable structure, lightweight, easy processing, and environmental friendliness. However, designing multifunctional molecular ferroelectrics with excellent properties has always been a great challenge. Herein, a multiaxial molecular ferroelectric is successfully designed by modifying the quasi-spherical cation dabco with CuBr2 to obtain halogenated [Bretdabco]CuBr4 (Bretdabco = N-bromoethyl-N'-diazabicyclo [2.2.2]octane), which crystallizes in polar point groups (C6). Typical ferroelectric behaviors featured by the P-E hysteresis loop and switched ferroelectric domain are exhibited. Notably, the molecular ferroelectric shows a high TC of 460 K, which is rare in the field and could greatly expand the application range of this material. In addition, the band gap is adjustable through the regulation of halogen. Both the UV absorption spectra and theoretical calculations indicate that the molecular ferroelectrics belong to a direct band gap (2.14 eV) semiconductor. This tunable and narrow band gap semiconductor molecular ferroelectric material with high TC can be utilized more effectively in the study of optoelectronics and sensors, including piezoelectric energy harvesters. This research may provide a promising approach for the development of multiaxial molecular ferroelectrics with a tiny band gap and high TC.

1D Chiral Enantiomer Lead-Free Perovskites Induced Chiralopical Activity and Photoelectric Response.

Chirality is a fascinating geometrical concept with widespread applications in biology, chemistry, and materials. Incorporating chirality into hybrid perovskite materials can induce novel physical properties (chiral optical activity, nonlinear optics, etc.). Hybrid lead-free or lead-substituted perovskite materials, as representatives of perovskites, have been widely used in fields such as photovoltaics, sensors, catalysis, and detectors. However, the successful introduction of chirality into hybrid lead-free perovskites, which can enable their potential applications in areas such as circularly polarized light photodetectors, memories, and spin transistors, remains a challenging research topic. Here, we synthesized two new chiral lead-free perovskites, [(R)-2-methylpiperazine][BiI5] and [(S)-2-methylpiperazine][BiI5]. The material possesses a perovskite structure with a one-dimensional (1D) arrangement, denoted as ABX5. This structure is composed of chiral cations, specifically methylpiperazine, and endless chains of [BiI3] along the a-axis. These chains are assembled from distorted coplanar [BiI5]2- octahedra. The testing results revealed that (R)-1 and (S)-1 have narrow band gaps (Eg-R = 2.016 eV, Eg-S = 1.964 eV), high photoelectric response, and long carrier lifetime [R = 4.94 µs (τ), S = 7.85 µs (τ)]. It is worth noting that 1D chiral lead-free perovskites (R)-1 and (S)-1, which are synthesized in this study with narrow band gaps, high photoelectric response, and long carrier lifetime, have the potential to serve as alternative materials for the perovskite layer in future iterations of lead-free perovskite solar cells. Moreover, this research will inspire the preparation of multifunctional, lead-free perovskites.

Ni/Fe layered double hydroxide nanosheet/G-quadruplex as a new complex DNAzyme with highly enhanced peroxidase-mimic activity.

A novel and low-cost DNAzyme, Ni/Fe layered double hydroxide (LDH) nanosheet/G-quadruplex (without hemin) with enhanced peroxidase-mimic activity was designed. The catalytic mechanism was investigated. The detection of Cu(II) in actual serum samples could be realized sensitively via this efficient DNAzyme-based method.

Three Robust Blue-Emitting Anionic Metal-Organic Frameworks with High Stability and Good Proton Conductivities.

Three anionic luminescent metal-organic frameworks (LMOFs; [M(tcbpe)(CH3)2NH2]·H2O; M = In3+, Eu3+, Gd3+; tcbpe = 4',4‴,4‴″,4‴‴'-(ethene-1,1,2,2-tetrayl)tetrakis[(1,1'-biphenyl)-4-carboxylic acid]) are synthesized by employing the tetraphenylethene core ligand H4tcbpe with M3+ ions. They stack in the similarly 4-fold-interpenetrated three-dimensional porous structure. All give blue emission when excited at 365 nm, with fluorescence quantum yields of 34.8% (MOF-In), 7.1% (MOF-Eu), and 28.1% (MOF-Gd). Somewhat surprisingly, these three complexes are extremely stable both in various solvents and across a broad pH range: MOF-In is stable between pH = 0 and 14, and MOF-Eu and MOF-Gd are stable between pH = 0 and 13. Additionally, they also show good proton conductivities of 2.29 × 10-5 S·cm-1 (MOF-In), 2.02 × 10-4 S·cm-1 (MOF-Eu), and 1.24 × 10-4 S·cm-1 (MOF-Gd) at high temperature under 98% relative humidity. To the best of our knowledge, this is the first reported LMOF series combining aggregation-induced emission behavior with good proton conductivities.

Precise Molecular Design Toward Organic-Inorganic Zinc Chloride ABX3 Ferroelectrics.

Organic-inorganic ABX3 (A, B = cations, X = anion) hybrids with perovskite structure have recently attracted tremendous interest due to their structural tunability and rich functional properties, such as ferroelectricity. However, ABX3 hybrid ferroelectrics with other structures have rarely been reported. Here, we successfully designed an ABX3 hybrid ferroelectric [(CH3)3NCH2F]ZnCl3 with a spontaneous polarization of 4.8 µC/cm2 by the molecular modification of [(CH3)4N]ZnCl3 through hydrogen/halogen substitution. It is the first zinc halide ABX3 ferroelectric, which contains one-dimensional [ZnCl3]-n chains of corner-sharing ZnCl4 tetrahedra, distinct from the anionic framework of corner-sharing or face-sharing BX6 octahedra in the ABX3 perovskites. From zero dimension to one dimension, the high symmetry of ZnCl4 tetrahedra is broken, and all of them align along one direction to form a polar [ZnCl3]-n chain, beneficial to the generation of ferroelectricity. This finding provides an efficient polar anionic framework for enriching the family of hybrid ferroelectrics by assembling with various cations and should inspire further exploration of new classes of organic-inorganic ABX3 ferroelectrics.

Fe-Doped CoP Flower-Like Microstructure on Carbon Membrane as Integrated Electrode with Enhanced Sodium Ion Storage.

Poor cyclability and rate performance always impede the development of transition metal phosphide-based anode materials. Many strategies have been used to address the above problems, such as the designing of hierarchical structures, combination with carbon materials, and doping with other metal elements. Considering those strategies, a flower-like Fe-doped CoP material is designed. The synthesis consists of microsheets grown on a carbon membrane (CM, leaves as precursor) through a hydrothermal method and in situ phosphorization. The Fe doping and carbon membrane synergistically induce the formation of a flower-like hierarchical microstructure during the crystal-growing process. The unique hierarchical microstructure increases the contact area between electrode and electrolyte, and accommodates the volume expansion during cycling. The hierarchical Fe-doped CoP grown directly on the carbon membrane increases the active sites for intercalation of sodium species and further promotes the internal electron conduction in the Fe-doped CoP/CM electrode. Thereby, the Fe-doped CoP/CM as the anode electrode for sodium ion batteries exhibits a high specific capacity of 515 mA h g-1 at 100 mA g-1 after 100 cycles. Even if the current density rises to 500 mA g-1 , the specific capacity is still maintained at 324 mA h g-1 after 500 cycles, showing superior rate performances and cyclability.

Synthesis and biological evaluation of calycanthaceous alkaloid analogs.

Starting from 9-methyl-1,2,3,4,9,9a-hexahydro-4aH-pyrido[2,3-b]indol-4a-ol, or indole-3-acetonitrile, 40 new calycanthaceous alkaloid analogs were synthesized in excellent yields. The prepared compounds were evaluated for biological activity against acetylcholinesterase and a broad range of plant pathogen fungi. The results of bioassays indicated that the majority of tested compounds displayed comparable or better in vitro bioactivity than the positive control. Notably, compounds b8 and b9 showed higher activity against Verticillium dahlia than chlorothalonil, with MIC values of 62.5 and 7.81 µg mL-1, respectively. Compound b3 had a higher activity against Bacillus cereus, with a MIC value of 15.63 µg mL-1. Compounds c2 and c11 revealed potent activity against acetylcholinesterase, with MIC values of 0.01 and 0.1 ng mL-1, respectively. Analysis of the molecular docking modes of c2 and c11 with Torpedo californica acetylcholinesterase indicated a medium strong hydrogen bond interaction between the hydroxyl groups of both the ligands and the phenolic hydroxyl of Try121 at a distance of approximately 2.4 Å. The results obtained in this study will be useful for the further design and structural optimization of calycanthaceous alkaloids as potential agrochemical lead compounds for plant disease control.

Antimony-doped tin oxide nanoparticles as peroxidase mimics for paper-based colorimetric detection of glucose using smartphone read-out.

Antimony-doped tin oxide nanoparticles (ATO NPs) were loaded on a filter paper where they act as a peroxidase mimic without electrochemical or photochemical assistance. The peroxidase mimicking activity is distinctly improved compared to most known nanomaterials and to natural horseradish peroxidase. The catalytic properties depend on the amount of antimony doped into the ATO NPs. A glucose assay was worked out that is based on (a) the oxidation of glucose by glucose oxidase under formation of H2O2, (b) the oxidation of 3,3,5,5-tetramethybenzidine (TMB) catalyzed by ATO NPs to form blue-green colored oxidized TMB on the surface of the paper. The coloration was analyzed with a smartphone. The method has a 21 µM limit of detection and a linear range that extends from 0.5 to 80 mM. Graphical abstract Antimony-doped tin oxide nanoparticles (ATO NPs) combined with 3,3,5,5-tetramethybenzidine (TMB) and triethylamine were coated on the filter paper. After addition of sample solution, the blue-green colored oxidized TMB was generated and recorded by a digital camera.

Fluorometric determination of zinc(II) by using DNAzyme-modified magnetic microbeads.

A fluorometric assay for zinc ion is described that relies (a) on the use of an isothermal cycle to amplify the fluorescence signal, and (b) of magnetic beads (MBs) to completely remove unreacted DNA detection probes. Biotin and fluorophore-labeled substrate (Zn-Sub) strands acting as detection probes were first assembled on MBs. Next, Zn(II)-specific DNAzyme (Zn-Enz) strands were hybridized with the Zn-Sub strands. In the presence of Zn(II), the Zn-Sub strands are cleaved. This results in the release of the shorter DNA fragments (containing fluorescent label) and in the dissociation of Zn-Enz strands. The dissociated Zn-Enz strands then hybridize with the residual Zn-Sub strands and cleave them in a similar fashion. This leads to a target recycling amplification mechanism and in a cumulative signal amplification process. A strongly amplified signal is thus obtained in the presence of Zn(II). The use of MBs warrants that unreacted Zn-Sub strands can be magnetically separated from the solution. The method has a detection limit as low as 33 fM at a signal-to-noise ratio of 3 and a linear response in the 100 fM to 11 nM Zn(II) concentration range. It was applied to the determination of Zn(II) in spiked tap water and seawater samples, and the results compared well with data obtained by ICP-MS analysis. The method was also applied to the determination of Zn(II) in infant milk powder and breast milk. Graphical abstract Magnetic beads (MBs) carrying fluorescein-labeled substrate (Zn-Sub) strands were hybridized with Zn(II)-specific DNAzyme (Zn-Enz) and cleaved in the presence of Zn(II). After recycling, the unreacted Zn-Sub strands were removed with MBs and the released fluorescein tags are measured.

Temperature-triggered reversible dielectric and nonlinear optical switch based on the one-dimensional organic-inorganic hybrid phase transition compound [C6H11NH3]2CdCl4.

The one-dimensional organic-inorganic hybrid compound bis(cyclohexylammonium) tetrachlorocadmate(II) (1), in which the adjacent infinite [CdCl4]n(-) chains are connected to each other though Cd···Cl weak interactions to form perovskite-type layers of corner-sharing CdCl6 octahedra separated by cyclohexylammonium cation bilayers, was synthesized. It undergoes two successive structural phase transitions, at 215 and 367 K, which were confirmed by systematic characterizations including differential scanning calorimetry (DSC) measurements, variable-temperature structural analyses, and dielectric and second harmonic generation (SHG) measurements. A precise structural analysis discloses that the phase transition at 215 K is induced by the disorder-order transition of cyclohexylammonium cations, while the phase transition at 367 K derives from changes in the relative location of Cd atoms. Emphatically, both the dielectric constant and SHG intensity of 1 show a striking change between low and high states at around 367 K, which reveals that 1 might be considered as a potential dielectric and nonlinear optical (NLO) switch with high-temperature response characterization, excellent reversibility, and obvious change of states.

One Pot Synthesis of New Benzimidazole Derivatives with Exceptionally High Luminescence Quantum Efficiency.

AIM AND OBJECTIVES: There are different approaches to the synthesis of benzimidazole. In this article, five new benzimidazole derivatives, BMPO, Me-BMPO, Di-MeBMPO, F-BMPO and Cl-BMPO where (BMPO=3-[(1H)-benzo[d]imidazol-2-yl]pyridin-2(1H)-one), have been prepared. Another study was carried out on luminescence properties and their potential applications for the detection of transition metal ions. MATERIALS AND METHODS: From the one-pot synthesis approach, all the derivatives of the benzimidazole compounds were obtained. The compounds were characterized using HRMS, 1HNMR, 13CNMR, and X-ray crystallography. Herein, a mechanism has been deciphered by predicting the release of HCl(g). RESULTS: All compounds showed a strong deep blue emission when dissolved in dimethylacetamide (DMA), with emission wavelengths at 423, 428, 435, 423, and 421 nm, and half-times of 3.64, 2.77, 2, 19, 3.42 and 3.52 ns, respectively. In addition, their emission quantum yields were determined to be 72, 50, 42, 73 and 80%. CONCLUSION: Five new benzimidazole derivatives, BMPO, Me-BMPO, Di-MeBIPO, F-BIPO, and Cl-BIPO, have been successfully synthesized by the one-pot synthesis method, and their structures are characterized and confirmed. The compounds exhibited exceptional luminescence by emitting a strong blue light in DMA with high fluorescence quantum yields between 42~80%.

Heterogeneous bimetallic selenides encapsulated within graphene aerogel as advanced anodes for sodium ion batteries.

Metal selenides are promising anode candidates for sodium ion batteries (SIBs) because of their high theoretical capacity, low cost, and environmental friendship. However, the low rate capability at high current density due to its inherent low electrical conductivity and poor cycle stability caused by inevitable volume variations during cycling frustrate its practical applications. Herein, we have developed a simple metallic-organic frameworks (MOFs)-derived selenide strategy to synthesize a series of heterogeneous bimetallic selenides encapsulated within graphene aerogels (GA) as anodes for SIBs. The bimetallic selenides/GA composites have unique structural characteristics that can shorten the migration path for Na+/electrons and accommodate the volume variations via additional void space during cycling. The built-in electric fields induced at the heterointerfaces can greatly reduce the activation energy for rapid charge transfer kinetics and promote the diffusion of Na+/electrons. GA is also beneficial for accommodating the volume variations during cycling and improving conductivity. As an advanced anode for SIBs, the MoSe2-Cu1.82Se@GA with a special porous octahedron can deliver the highest capacity of 444.8 mAh/g at a high rate of 1 A/g even after 1000 cycles among the bimetallic selenides/GA composites.

1,1'-(Ethane-1,2-di-yl)dipyridinium bis-(1,2-di-cyano-ethene-1,2-di-thiol-ato-κ(2) S,S')cuprate(II).

In the title ion-pair complex, (C12H14N2)[Cu(C4N2S2)2], the complex anion exhibits a highly twisted coordination environment around the tetra-coordinated Cu(II) atom. The dihedral angles between the 1,2-di-cyano-ethene-1,2-di-thiol-ato ligands and between the two pyridine rings in the cation are 37.49 (3) and 29.18 (10)°, respectively. Weak C-H⋯N and C-H⋯S hydrogen bonds link the cations and anions into a three-dimensional network.

Efficient C2H6/C2H4 adsorption separation by a microporous heterometal-organic framework.

Purification of ethylene (C2H4) is an essential and energy-intensive process in the petrochemical industry. Adsorption separation using ethane (C2H6)-selective porous adsorbents is a highly efficient and straightforward method for obtaining polymer-grade C2H4 from a binary C2H6/C2H4 mixture. However, the design and construction of C2H6-selective adsorbents are very challenging tasks. Herein, we demonstrate a microporous heterometal-organic framework, CuIn(ina)4, can preferentially enrich C2H6 than C2H4. Experimental results revealed that CuIn(ina)4 exhibited remarkable separation performance for the C2H6/C2H4 mixture with a high C2H6 loading capacity (3.3 mmol/g), high IAST selectivity (2.3) and separation potential (1578 mmol/L for equimolar C2H6/C2H4 mixture) under ambient conditions. The effectiveness of CuIn(ina)4 for C2H6/C2H4 adsorption separation was confirmed by theoretical calculations and breakthrough experiments.

An integrated process for struvite recovery and nutrient removal from ship domestic sewage.

Marine pollution caused by the untreated and substandard discharge of ship domestic sewage has received widespread attention. A novel integrated process for struvite recovery and nutrient removal from ship domestic sewage (SRNR-SDS) based on seawater magnesium source was developed in this study. Removal efficiencies of the total nitrogen (TN) and total phosphorus (TP) for the activated sludge unit in SRNR-SDS process were approximately 67.61% and 41.35%, respectively, under the salinity of 7.85 g/L. The coupling-induced struvite crystallization unit significantly improved the removal efficiency of TN and TP, and the scanning electron microscopy and X-ray diffraction demonstrated that magnesium ammonium phosphate (MAP) crystals were successfully formed on the surface of zeolite. The SRNR-SDS process had an ideal performance for pollutant removal and MAP recovery under the optimal hydraulic retention time of 20 h. The effluent concentrations of COD, NH4+-N, TN and TP in SRNR-SDS process were approximately 34.73 mg/L, 4.31 mg/L, 10.07 mg/L and 0.23 mg/L, respectively, which meet the Chinese and international ship sewage discharge standards. SRNR-SDS process has obvious environmental, social and economic benefits, which could save 6.20%∼57.14% of the operation cost of ship domestic sewage treatment via MAP recovery. The results could provide theoretical and technical support for the development and application of ship sewage treatment process with the functions of pollutant removal and resource recovery.

Realizing near white and warm light emission of cuprous iodide complexes by alkyl-isomerization of ligands.

Four novel all-in-one structured cuprous iodide hybrid materials are presented. Isomerization of the alkyl chain on the ligand improved material thermal stability and regulated their luminescence to warm and near-white light emission, with the internal quantum yield increasing from 5% to 83%. This provides a reasonable route for designing white light emitting cuprous iodide materials for solid-state lighting in future.

Dimorpholinium tetra-chlorido-cobaltate(II).

In the title mol-ecular salt, (C(4)H(10)NO)(2)[CoCl(4)], the morpholinium cations adopt chair conformations and the tetra-chloridocobaltate(II) anion is significantly distorted from regular tetra-hedral geometry [Cl-Co-Cl = 102.183 (19)-117.59 (2)°]. The Co-Cl bond lengths for the chloride ions not accepting hydrogen bonds are significantly shorter than those for the chloride ions accepting such bonds. In the crystal, the components are linked by N-H⋯O and N-H⋯Cl and bifurcated N-H⋯(O,Cl) hydrogen bonds to generate (100) sheets.

2-[(4-Chloro-anilino)meth-yl]phenol.

In the title compound, C(13)H(12)ClNO, the dihedral angle between the two benzene ring planes is 68.71 (8)°. In the crystal, mol-ecules are linked by pairs of O-H⋯N hydrogen bonds into inversion dimers, which are further linked by intermolecular N-H⋯O interactions into a chain running parallel to the a axis.