Sr2[B5O8(OH)]2 ⋠[B(OH)3] ⋠H2O: A Strontium Borate That Shows Deep-Ultraviolet-Transparent Nonlinear Optical Properties.

A new noncentrosymmetric strontium borate, P1-Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O (1), has been synthesized under the hydrothermal condition. The P1-Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O shows a layered B-O network with 9-ring windows in the ab plane. Sr2+ cations, H3BO3, and H2O molecules are located in the voids of layers and interlayers, respectively. The P1-Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O is the first synthetic phase of veatchite, while the other three polymorphs are found in different natural minerals. This strontium borate is a potential deep-ultraviolet-transparent nonlinear-optical (NLO) crystal whose second-harmonic-generation (SHG) intensity is 1.7 times that of KH2PO4 (KDP) and is phase-matchable. The short wavelength cutoff edge of compound 1 is below 190 nm. Density functional theory (DFT) calculations show that the B-O units are responsible for the nonlinear optical property.

Lewis Acid Decorated Hexacyanodiborane(6) Dianion.

First examples of diborane(6) dianions decorated with weakly coordination B(C6F5)3 (BCF) groups and SiEt3 + moieties have been synthesized demonstrating the synthetic potential of the [B2(CN)6]2- dianion. [B2{CNB(C6F5)3}6]2- (1) was isolated as potassium and tetrabutylammonium salt. 1 is a rare example for a weakly coordinating dianion and it was used for the stabilization of the carbocation [Ph3C]+ and the oxonium acid [H(OEt2)2]+. Reaction of [Ph3C]21 with HSiEt3 resulted in the silylated neutral diborane(6) [B2{CNB(C6F5)3}4(CNSiEt3)2] (2) in which two BCF groups have been selectively replaced by SiEt3 + substituents, underscoring the stability and chemical versatility of the [B2(CN)6]2- dianion. The chemical properties and physicochemical data of 1 and 2 provide insight into electronic, coordinating, and steric properties of theses novel diborane(6) compounds.

Thermodynamic Properties and DFT Study on Highly Frustrated Cr3BO6: Coexistence of Spin-Singlets with Long-Range Magnetic Order.

The triangle-based magnetic subsystem of borates with the mineral norbergite structure M3BO6 (M = Fe, Cr, V) makes these compounds unique to investigate rare quantum ground states influenced by strong magnetic frustration. In this work, we investigated the thermal and magnetic properties of Cr3BO6 to find that despite very large negative Weiss temperature Θ = -160.7 K, it orders only at TN = 4.5 K and experiences a spin-flop transition at µ0H = 5 T. Density functional theory (DFT) calculations of exchange interaction parameters allow for suggesting the model of magnetic subsystem in chromium borate Cr3BO6. The results prove the decisive role of magnetic frustration on the formation of long-range order, providing therefore a basis for future study. Both experimental data and first-principles calculations point to the coexistence of chromium spin-singlets with long-range antiferromagnetic order.

Ba4 B14 O25 : A Deep Ultraviolet Transparent Nonlinear Optical Crystal with Strong Second Harmonic Generation Response Achieved by a Boron-Rich Closed-Loop Strategy.

Discovering new deep ultraviolet (DUV) nonlinear optical (NLO) materials is the current research hotspot. However, how to perfectly integrate several stringent performances into a crystal is a great challenge because of the natural incompatibility among them, particularly wide band gap and large NLO coefficient. To tackle the challenge, a boron-rich closed-loop strategy is supposed, based on which a new barium borate, Ba4 B14 O25 , is designed and synthesized successfully via the high-temperature solid-state melting method. It features a highly polymeric 3D geometry with the closed-loop anionic framework [B14 O25 ]8- constructed by the fundamental building blocks [B14 O33 ]24- . The high-density π-conjugated [BO3 ]3- groups and the fully closed-loop B-O-B connections make Ba4 B14 O25 possess excellent NLO properties, including short UV cutoff edge (<200 nm), large second harmonic generation response (3.0 × KDP) and phase-matching capability, being a promising DUV-transparent NLO candidate material. The work provides a creative design strategy for the exploration of DUV NLO crystals.

Borate-Based Artificial Solid-Electrolyte Interphase Enabling Stable Lithium Metal Anodes.

Lithium (Li) metal is considered as the "holy grail" of anode materials for next-generation high energy batteries. However, notorious dendrite growth and interfacial instability could induce irreversible capacity loss and safety issues, limiting the practical application of Li metal anodes. Herein, we develop a novel approach to construct a borate-based artificial solid-electrolyte interphase (designated as B-SEI) through the reaction of metallic Li with triethylamine borane (TEAB). According to our cryogenic electron microscopy (Cryo-EM) characterization results, the artificial SEI adopts a glass-crystal bilayer structure, which facilitates uniform Li-ion transport and inhibits dendrite growth during Li plating. Benefiting from such an artificial SEI, the Li anode delivers an improved rate performance and prolonged cycle life. The symmetric Li/B-SEI||Li/B-SEI cell can maintain stable cycling for 700 h at a high current density of 3 mA cm-2. The full-cell pairing Li/B-SEI with LiFePO4 only exhibits minimal capacity decay after 500 cycles in a conventional carbonate-based electrolyte. This work demonstrates the feasibility of building a boride-based artificial SEI to stabilize the Li metal anode based on microscopic characterization results and comprehensive electrochemical data, which represents a promising avenue to develop practical Li metal batteries.

The Effect of Rare-Earth Elements on the Morphological Aspect of Borate and Electrocatalytic Sensing of Biological Compounds.

Adjusting the morphological characteristics of a material can result in improved electrocatalytic capabilities of the material itself. An example of this is the introduction of rare-earth elements into the borate structure, which gives a new perspective on the possibilities of this type of material in the field of (bio)sensing. In this paper, we present the preparation of borates including La, Nd and Dy and their application for the modification of a glassy carbon electrode, which is used for the non-enzymatic detection of a biologically relevant molecule, vitamin B6 (pyridoxine). Compared with the others, dysprosium borate has the best electrocatalytic performance, showing the highest current and the lowest impedance, respectively, as determined using cyclic voltammetry and impedance tests. Quantitative testing of B6 was performed in DPV mode in a Britton-Robinson buffer solution with a pH of 6 and an oxidation potential of about +0.8 V. The calibration graph for the evaluation of B6 has a linear range from 1 to 100 µM, with a correlation coefficient of 0.9985 and a detection limit of 0.051 µM. The DyBO3-modified electrode can be used repeatedly, retaining more than 90% of the initial signal level after six cycles. The satisfactory selectivity offered a potential practical application of the chosen method for the monitoring of pyridoxine in artificially prepared biological fluids with acceptable recovery. In light of all the obtained results, this paper shows an important approach for the successful design of electrocatalysts with tuned architecture and opens new strategies for the development of materials for the needs of electrochemical (bio)sensing.

The synthesis of novel lanthanum hydroxyborate at extreme conditions.

The novel structure of lanthanum hydroxyborate La2B2O5(OH)2 was synthesized by the reaction of partially hydrolyzed lanthanum and boron oxide in a diamond anvil cell under high-pressure/high-temperature (HPHT) conditions of 30 GPa and ∼2,400 K. The single-crystal X-ray structure determination of the lanthanum hydroxyborate revealed: P3¯c1, a = 6.555(2) Å, c = 17.485(8) Å, Z = 6, R1 = 0.056. The three-dimensional structure consists of discrete planar BO3 groups and three crystallographically different La ions: one is surrounded by 9, one by 10, and one by 12 oxygen anions. The band gap was estimated using ab initio calculations to be 4.64 eV at ambient pressure and 5.26 eV at 30 GPa. The current work describes the novel HPHT lanthanum hydroxyborate with potential application as a deep-ultraviolet birefringent material.

The Synthesis, Structure, and Luminescent Properties of TmMgB5O10 Crystals.

TmMgB5O10 spontaneous crystals were synthesized via the flux-growth technique from a K2Mo3O10-based solvent. The crystal structure of the compound was solved and refined within the space group P21/n. The first principles calculations of the electronic structure reveal that TmMg-pentaborate with an ideal not defected crystal structure is an insulator with an indirect energy band gap of approximately 6.37 eV. Differential scanning calorimetry measurements and powder X-ray diffraction studies of heat-treated solids show that TmMgB5O10 is an incongruent melting compound. A characteristic band of the Tm3+ cation corresponding to the 3H6 → 1D2 transition is observed in the photoluminescence excitation spectra of TmMg-borate. The as-obtained crystals exhibit intense blue emission with the emission peaks centered at 455, 479, 667, and 753 nm. The most intensive band corresponds to the 1D2 → 3F4 transition. TmMgB5O10 solids demonstrate the thermal stability of photoluminescence.

A Photoluminescence Study of Eu3+, Tb3+, Ce3+ Emission in Doped Crystals of Strontium-Barium Fluoride Borate Solid Solution Ba4-xSr3+x(BO3)4-yF2+3y (BSBF).

The present study is aimed at unveiling the luminescence potential of Ba4-xSr3+x(BO3)4-yF2+3y (BSBF) crystals doped with Eu3+, Tb3+, and Ce3+. Owing to the incongruent melting character of the phase, the NaF compound was used as a solvent for BSBF crystal growth. The structure of BSBF: Eu3+ with Eu2O3 concentration of about 0.7(3) wt% was solved in the non-centrosymmetric point group P63mc. The presence of Eu2O3 in BSBF: Eu3+ leads to a shift of the absorption edge from 225 nm to 320 nm. The photoluminescence properties of the BSBF: Ce3+, BSBF: Tb3+, BSBF: Eu3+, and BSBF: Eu3+, Tb3+, Ce3+ crystals have been studied. The unusual feature of europium emission in BSBF is the intensively manifested 5D0→7F0 transition at about 574 nm, which is the strongest for BSBF: Eu3+ at 370 nm excitation and for BSBF: Eu3+, Tb3+, Ce3+ at 300 nm and 370 nm excitations. No evidence of Tb3+→Eu3+ energy transfer was found for BSBF: Eu3+, Tb3+, Ce3+. The PL spectra of BSBF: Eu3+ at 77 and 300 K are similar with CIE chromaticity coordinates of (0.617; 0.378) at 300 nm excitation and (0.634; 0.359) at 395 nm excitation and low correlated color temperature which implies application prospects in the field of lightning. Due to the high intensity of 5D0→7F0 Eu3+ transition at 370 nm excitation, the BSBF: Eu3+ emission is yellow-shifted.

Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers.

Despite large-scale investigations of homogeneous single-site metallocene catalysts and systems based on them, there are still unsolved problems related to the control of their activity and chemo- and stereoselectivity. A solution to these problems is required to develop efficient methods for the synthesis of practically useful products of alkene transformations, such as dimers, oligomers, and polymers. Here we studied the catalytic activity of structurally diverse zirconocenes (L2ZrCl2, L = Cp, C5Me5, Ind, L2 = Me2CCp2, Me2SiCp2, Me2C2Cp2, rac-Me2CInd2, rac-H4C2Ind2, BIPh(Ind)2, H4C2[THInd]2), and co-catalysts activating the system, namely HAlBui2, MMAO-12, and (Ph3C)[B(C6F5)4], at low activator/Zr ratios in a 1-hexene oligomerization reaction. The influence of catalyst structure and system composition on the alkene conversion, the type of products, and the reaction stereoselectivity were investigated. The composition of hydride intermediates formed in the L2ZrCl2-HAlBui2-activator system (L2 = ansa-Me2CCp2, Ind) was studied by NMR spectroscopy. Participation of the bis-zirconium hydride complex as the precursor of catalytically active sites of the alkene dimerization reaction was shown.

Incorporation of Bismuth Increases the Electrocatalytic Activity of Cobalt Borates for Oxygen Evolution Reaction.

The development of durable and efficient electrocatalysts composed of low-cost, earth-abundant metals for the oxygen evolution reaction (OER) is crucial for industrial-scale water splitting to produce green hydrogen on a large scale. Transition metal borates are considered good candidate electrocatalysts for OER due to their low cost, ease of synthesis, and good catalytic activity. In this work, we demonstrate that the incorporation of an oxophilic main group metal, bismuth (Bi), into cobalt borates produces highly effective electrocatalysts for OER. We also show that the catalytic activity of Bi-doped cobalt borates can be improved further by pyrolyzing them in an argon atmosphere. During pyrolysis, the Bi crystallites formed in the materials melt, transform into amorphous phases, interact better with the Co or B atoms in there, and form more synergistic catalytic sites for OER. By varying the amount of Bi as well as the pyrolysis temperature, different Bi-doped cobalt borates are synthesized, and the most optimal OER electrocatalyst is identified. Among them, the one with Co : Bi ratio of 9 : 1 and that is pyrolyzed at 450 °C exhibits the best catalytic activity, driving the reaction at a current density of 10 mA cm-2 with the lowest overpotential (318 mV) and a Tafel slope of 37 mV dec-1 .

Phase Relations in the Ln2O3-Cr2O3-B2O3 (Ln = Gd-Lu) Ternary Oxide Systems.

In this work, isothermal sections of the Ln2O3-Cr2O3-B2O3 (Ln = Gd-Lu) ternary oxide systems at 900, 1000, and 1100 °C were constructed by determining the phase relations by using a powder X-ray diffraction technique. As a result, these systems were divided into subsidiary subsystems. Two types of double borates, LnCr3(BO3)4 (Ln = Gd-Er) and LnCr(BO3)2 (Ln = Ho-Lu), were observed in the investigated systems. Regions of phase stability for LnCr3(BO3)4 and LnCr(BO3)2 were determined. It was shown that the LnCr3(BO3)4 compounds crystallized in rhombohedral and monoclinic polytype modifications up to 1100 °C; above this temperature and up to the melting points, the monoclinic modification was predominantly formed. The LnCr3(BO3)4 (Ln = Gd-Er) and LnCr(BO3)2 (Ln = Ho-Lu) compounds were characterized by using a powder X-ray diffraction method and thermal analysis.

Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]-: Theoretical and Experimental Study.

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]- was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]- and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]-. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]- was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.

Co2+ to Al3+ Substitution Induced Dual-Site Synergistic Catalysis to Friedel-Crafts Alkylation Reactions.

The dual-site synergistic effect in heterogeneous catalysis is quite interesting, and also complex because at least two substrate molecules are adsorbed or activated on the catalyst surface, which apparently needs two spatially separated and functionally independent active sites. It would become more difficult when the substrate molecules are large ones. The replacement of Al3+ in Al4 B6 O15 lattice with Co2+ leads to the formation of unsaturated Co2+ (4-fold coordination) along with oxygen vacancies (Ov ). The former one behaves as a medium-strength Lewis acid site, and can adsorb and activate molecules with a nitro group (e. g., ß-nitrostyrene). The latter one can adsorb and activate oxygen species, which further activates the indole derivatives. Next, the spatially separated dual sites on the catalyst surface can synergistically and efficiently catalyze their Friedel-Crafts alkylation reactions under mild conditions. The high durability can be proved by the as-maintained high yields, that is, 98, 93, 96, 92 and 90 % for 5 runs, respectively. The reaction kinetics obey the second-order characteristic. Annealing under hydrogen condition can further generate more surficial Ov , leading to an improvement to the catalytic activity. A simple and probably routine aliovalent doping endows such a complex synergistic catalysis involving two large substrate molecules, providing an inspired perspective of developing dual-site catalysts.

Arrhenius Crossover Temperature of Glass-Forming Liquids Predicted by an Artificial Neural Network.

The Arrhenius crossover temperature, TA, corresponds to a thermodynamic state wherein the atomistic dynamics of a liquid becomes heterogeneous and cooperative; and the activation barrier of diffusion dynamics becomes temperature-dependent at temperatures below TA. The theoretical estimation of this temperature is difficult for some types of materials, especially silicates and borates. In these materials, self-diffusion as a function of the temperature T is reproduced by the Arrhenius law, where the activation barrier practically independent on the temperature T. The purpose of the present work was to establish the relationship between the Arrhenius crossover temperature TA and the physical properties of liquids directly related to their glass-forming ability. Using a machine learning model, the crossover temperature TA was calculated for silicates, borates, organic compounds and metal melts of various compositions. The empirical values of the glass transition temperature Tg, the melting temperature Tm, the ratio of these temperatures Tg/Tm and the fragility index m were applied as input parameters. It has been established that the temperatures Tg and Tm are significant parameters, whereas their ratio Tg/Tm and the fragility index m do not correlate much with the temperature TA. An important result of the present work is the analytical equation relating the temperatures Tg, Tm and TA, and that, from the algebraic point of view, is the equation for a second-order curved surface. It was shown that this equation allows one to correctly estimate the temperature TA for a large class of materials, regardless of their compositions and glass-forming abilities.

Rational Screening of Artificial Solid Electrolyte Interphases on Zn for Ultrahigh-Rate and Long-Life Aqueous Batteries.

Solid electrolyte interphase (SEI) on Zn anodes plays a pivotal role for high-rate and long-life aqueous batteries, because it effectively inhibits side reactions and dendritic growth. Many materials are explored as SEIs by a trial-and-error approach. Herein, an exercisable way is proposed to screen the potential SEIs on Zn anodes in view of dendrite-suppressing ability and charge-transfer property theoretically. As an output of this screening, Zn3 (BO3 )2 (ZBO) is checked experimentally. In symmetrical cells, Zn@ZBO runs over 250 h at an ultrahigh current density of 50 mA cm-2 for a large areal capacity 10 mAh cm-2 . In full cells, Zn@ZBO||MnO2 shows an impressive cumulative capacity (≈406 mAh cm-2 ) under harsh conditions, i.e., a lean electrolyte condition (10 µL mAh-1 ), limited Zn supply (negative/positive electrode capacity ratio, N/P ratio = 2.3), and high areal capacity (5.0 mAh cm-2 ). The significance of this work lies in not only the first report of ZBO on Zn showing excellent electrochemical performance, but also a feasible way to screen the promising SEI materials for other metal anodes.

Copper-Catalyzed Stereoselective Borylation and Palladium-Catalyzed Stereospecific Cross-Coupling to Give Aryl C-Glycosides.

Metabolically stable C-glycosides are an essential family of compounds in bioactive natural products, therapeutic agents, and biological probes. For their application, development of synthetic methods by connecting glycosides and aglycons with strict stereocontrol at the anomeric carbon, as well as with high functional-group compatibility and environmental compatibility is a pivotal issue. Although Suzuki-Miyaura-type C(sp3 )-C(sp2 ) cross-coupling using glycosyl boronates is a potential candidate for the construction of C-glycosides, neither the cross-coupling itself nor the facile synthesis of the coupling precursor, glycosyl boronates, have been achieved to date. Herein, it was succeeded to develop a copper-catalyzed stereoselective one-step borylation of glycosyl bromides to glycosyl boronates and palladium-catalyzed stereospecific cross-coupling of ß-glycosyl borates with aryl bromides to give aryl ß-C-glycosides, in which the ß-configuration of the anomeric carbon of the glycosyl trifluoroborates is stereoretentively transferred to that of the resulting aryl C-glycosides.

Assessing the bleaching effect of an experimental stabilized chlorine dioxide agent used for internal bleaching purposes

Aim Assessing the intracoronal bleaching effectiveness of an experimental chlorine dioxide product, based on the walking bleach technique. Methods Extracted bovine incisors were artificially stained with bovine blood and filled with zinc phosphate cement at cementoenamel junction level. Teeth were divided into 3 groups (n=10): (SP) sodium perborate added with distilled water, (CD) chlorine dioxide and (C) control - dry cotton inserted into the pulp chamber. Bleaching agents were used at 0, 7 and 14 days. VITA Easyshadetm (∆Eab) was used to analyze tooth color at the 7th, 14th and 21st days, based on the CIE2000 system. Data were analyzed through ANOVA and Tukey's test. Results There were no statistically significant differences in Δb, ΔE, ΔE00 and ΔWID between CD and the control group. These parameters have shown significant differences between CD and SP, which differed from the control. However, they did not show significant differences either in the control group or in CD at the 7th, 14th and 21st days. Values recorded for SP at the 7th day differed from those recorded at the 14th and 21st days. Δa has shown differences within the same group at the 7th, 14th and 21st days. There was no difference between groups, when they were compared at the same day (7th and 14th). The control group differed from SP at the 21st day. CD did not differ from the other two groups. ΔL did not show differences between groups and times. Conclusion Stabilized chlorine dioxide (0.07%, at pH 3.5) should not be used as intracoronal bleaching agent along with the walking bleach technique.

Rare Earth Complexes of Europium(II) and Substituted Bis(pyrazolyl)borates with High Photoluminescence Efficiency.

Rare earth europium(II) complexes based on d-f transition luminescence have characteristics of broad emission spectra, tunable emission colors and short excited state lifetimes, showing great potential in display, lighting and other fields. In this work, four complexes of Eu(II) and bis(pyrazolyl)borate ligands, where pyrazolyl stands for pyrazolyl, 3-methylpyrazolyl, 3,5-dimethylpyrazolyl or 3-trifluoromethylpyrazole, were designed and synthesized. Due to the varied steric hindrance of the ligands, different numbers of solvent molecules (tetrahydrofuran) are participated to saturate the coordination structure. These complexes showed blue-green to yellow emissions with maximum wavelength in the range of 490-560 nm, and short excited state lifetimes of 30-540 ns. Among them, the highest photoluminescence quantum yield can reach 100%. In addition, when the complexes were heated under vacuum or nitrogen atmosphere, they finally transformed into the complexes of Eu(II) and corresponding tri(pyrazolyl)borate ligands and sublimated away.

Design, Fabrication and Characterization of Biodegradable Composites Containing Closo-Borates as Potential Materials for Boron Neutron Capture Therapy.

Boron neutron capture therapy (BNCT) has been recognized as a very promising approach for cancer treatment. In the case of osteosarcoma, boron-containing scaffolds can be a powerful tool to combine boron delivery to the tumor cells and the repair of postoperative bone defects. Here we describe the fabrication and characterization of novel biodegradable polymer composites as films and 3D-printed matrices based on aliphatic polyesters containing closo-borates (CB) for BNCT. Different approaches to the fabrication of composites have been applied, and the mechanical properties of these composites, kinetics of their degradation, and the release of closo-borate have been studied. The most complex scaffold was a 3D-printed poly(ε-caprolactone) matrix filled with CB-containing alginate/gelatin hydrogel to enhance biocompatibility. The results obtained allowed us to confirm the high potential of the developed composite materials for application in BNCT and bone tissue regeneration.