Bond Valence Sum Research Articles

Structure-Photoluminescence Relationship in Ce3+-Doped K5Y(P2O7)2 and Its Sensitization to Dy3+ with Enhanced White Light Emission.

From a fundamental point of view, the structure-photoluminescence relationship is vitally important for developing efficient phosphors and rationally improving their performances. In this work, Rietveld refinements on high-resolution powder X-ray diffraction (XRD) data were conducted to verify the Ce3+ distribution in K5Y(P2O7)2 (KYPO). Ce3+ ions are located at both M1 and M2 sites, with occupation factors of 0.31(2) and 0.19(2), respectively. Importantly, the crystal field strength (CFS) is stronger at the former site due to the larger bond valence sum. Correspondingly, the Ce3+ emission can be deconvoluted into four Gaussian-type bands centered at ∼353, ∼383, ∼343, and ∼369 nm, where the former two belong to Ce3+ at the M1 site and the latter two are assigned to Ce3+ at the M2 site. Ce3+ in KYPO is a highly efficient activator, with optimal internal and external quantum efficiencies of 98.9 and 74.6%, respectively, and was thus utilized to sensitize the Dy3+ emission. Indeed, energy transfer from Ce3+ to Dy3+ was confirmed by fluorescent decay curves for Ce3+/Dy3+ codoped KYPO, and the mechanism was supposed to be dominated by dipole-dipole interactions. Indeed, it can be pumped by a 310 nm LED chip and emits a bright white light. Ce3+ photoluminescence exhibits high resistance to thermal quenching, and it can be further enhanced by codoping Dy3+, i.e. the emission intensity remains 96.3% at 423 K.

Crystal Structure and Li-Fe Order in Synthetic Mg(2-2x)LixFe3+x(SiO4) Olivine Structure.

Olivines are naturally occurring silicates consisting of isolated (SiO4)4- tetrahedra linked through M1O6 and M2O6 octahedra. In this study, we report the structural and crystal-chemical characterization of synthetic olivine crystals containing up to 25% Li-Fe3+ synthesized using the flux growth technique. Based on site scattering, <M1-O> and <M2-O> mean bond lengths, and charge neutrality of the chemical formula, we found a perfect ordering of Li and Fe3+ at the two distinct M1 and M2 sites. Unrestrained linear extrapolation to a hypothetical isostructural LiFe3+(SiO4) composition aligns well with the tabulated ionic radii of Li and Fe3+. Comparison made with the isostructural LiSc(SiO4) reveals that the Li-centered M2O6 octahedron has a significant capacity to distort in order to accommodate structural stresses, due to the relatively weak Li-O bond, while still achieving a bond valence sum that closely matches the formal charge of Li+. This behavior suggests the potential feasibility of an extended Li + Fe3+ for 2 Mg coupled substitution within the olivine structure. The reported structure of the LiFe3+(SiO4) endmember in the literature, despite its apparent matching of cell dimensions and space group with olivine, exhibits extremely unconventional crystal chemical features, raising questions about its validity. Given the importance of the suitability of Li-insertion in LiFeSiO4 as electrodes in rechargeable Li-ion batteries, further studies are needed to investigate its crystal structure and crystal chemistry.

Mongrel synthesis of tin (IV) based 3-aminopyridine with hydrogen halides: Structural, optical, thermal analysis, DFT, Hirshfeld surface analysis and antibacterial investigations

The novel organic-inorganic hybrid materials (C5H7N4)2 [SnCl6] 2- (1) and (C5H7N4)2 [SnBr6]2-(2) have been synthesized and characterized by single-crystal X-ray diffraction at room temperature. Both compounds demonstrate the crystal system was triclinic with Pī space group. Hirshfeld surface analysis investigate the intermolecular interactions and crystal packing derived by single-crystal XRD data reveals the closer contacts associated with strong interactions. Infrared spectrum of both compounds shows the NH stretching band at 3396 cm−1 which indicates a protonated amine group. The product crystals optical characteristics were inspected using UV–visible and photoluminescence spectroscopy. The thermal characteristics were evaluated simultaneously using thermogravimetric (TG) and differential thermal analysis. Tin formal oxidation state was determined as +4 through bond valence sum calculations and CSM shows the ideal octahedral geometry of the anions. DFT calculations utilizing the B3LYP method with the LanL2DZ basis set provide optimized geometries and molecular electrostatic potential maps. We explored the energy difference between (HOMO) and (LUMO) orbitals to understand molecular electrical transport capabilities. The biological activity of the investigated compounds are examined against pathogens which indicates efficacy against bacterial strains.

Synthetic V(V)-peroxido-zwitterionic species catalyze benzene oxidation under mild reaction conditions

A series of dinuclear complexes were synthesized, involving vanadium with N-methylglycine (sarcosine)/N,N’-dimethylglycine in aqueous media and H2O2, capable of exerting catalytic activity. Specifically, the ternary V(V) tetraperoxido dinuclear species (NH4)2[V2O2(O2)4(CH3NH2CH2COO)] (symmetric conformer) (1), (NH4)2[V2O2(O2)4(CH3NH2CH2COO)] (asymmetric conformer) (2), K2(Η2Ο)[V2O2(O2)4(CH3NH2CH2COO)] . H2O (3) (asymmetric conformer), and K2(Η2Ο)2[V2O2(O2)4{(CH3)2NHCH2COO)}] (4) (asymmetric conformer) were synthetically isolated in crystalline form. Compounds 1 and 2 are the same, whilst with profound conformational differences exemplified through pH-specific chemistries. The new materials 1–4 were characterized by elemental analysis, FT-IR, Raman, NMR, and UV–Visible spectroscopy, cyclic voltammetry, thermogravimetric analysis (TGA-DTG), and X-ray crystallography. Further support of the spectroscopic and structural profile was achieved through Bond Valence Sum (BVS) and Hirshfeld molecular mapping calculations. In all of the studied compounds, pH appears to be a crucial factor in the synthesis and isolation. The physicochemical characterization of the hybrid materials justified further use of compound 3 as a potential hydroxylation catalyst of benzene under a variable set of mild reaction conditions. The products of the catalytic reaction systems investigated were identified and quantified by gas chromatography–mass spectrometry (GC-MS) and gas chromatography–flame ionization detection (GC-FID), respectively. The results a) exemplify the involvement of the hybrid dinuclear vanadium compounds in the pursued benzene transformations, and b) distinctly demonstrate the structural and chemical characteristics justifying the emergence of catalytic action of vanadium under mild conditions (40 °C) in reactions toward organic substrates (e.g. benzene) as the basis for the pursuit of selective industrial applications, affording readily available useful compounds.

Broadband spectral cyan emission phosphor for full-spectrum LED caused by interstitial site occupation

The phosphor with a highly condensed, rigid framework structure and a single crystallographic site often exhibit symmetrical narrow-band emission. It is challenging to achieve broadband emission by doping Eu2+ ions in similar structures. Here, we propose to control the occupation and quenching concentration of Eu2+ ions in a single-site matrix Sc2Si2O7 to increase efficiency and precise regulation of luminescence spectra substantially. The analysis of photoluminescence spectroscopy through steady-state, transient-state, and Gaussian fitting techniques has discovered two emission centers despite the presence of a single rare-earth substitution site. The theoretical calculations and bond valence sum subsequently prove that Eu2+ ions prefer substituting the Sc3+ and interval sites to emit intense cyan light. Under 340 nm excitation, broad cyan-emission (FWHM = 115 nm) is exhibited with a high quantum yield of 60.67 %. The present phosphor exhibits pronounced thermal stability, and the emission intensity can still keep 68.3 % at 170 °C compared to that at atmospheric temperature. The Sc2Si2O7: Eu2+ phosphor boasts exceptional potential as a highly efficient cyan component in full-spectrum WLEDs. By replacing the blue light component commonly found in WLEDs, the intelligent and healthy alternative Sc2Si2O7: Eu2+ phosphor can effectively decrease the harmful blue light. This work also highlights the critical need to analyze local phosphor distortions upon rare-earth substitution, especially in single crystallographic site structures.

Exploring Phase Transition and Structural Complexity in the Mixed Cation Uranium Oxide CaUNb2O8.

The structures and high-temperature phase transition of CaUNb2O8 were studied in situ using synchrotron X-ray and neutron powder diffraction. Rietveld refinements provided an accurate description of the crystal structures of both the monoclinic fergusonite-type I2/b structure observed at room temperature and the tetragonal scheelite-type I41/a structure found at high temperatures. Bond valence sum analysis showed Nb5+ to be octahedrally coordinated in the monoclinic fergusonite-type structure, akin to other ANbO4 materials. Rietveld analysis of the variable temperature data allowed for the determination of accurate unit cell parameters and atomic coordinates, as well as revealing a reversible phase transition around ∼750 °C. The Nb-O bond distances display anomalous behavior, with a discontinuity in the longer Nb-O(1') distance coinciding with the phase transition suggestive of a reconstructive phase transition. Mode analysis identified the Γ2+ mode as the primary mode that drives the phase transition; this is linearly coupled to the induced spontaneous strain within the monoclinic fergusonite-type structure. Analysis of the temperature dependence of the Nb(z) positional parameter, as well as of the ϵ1-ϵ2 and ϵ6 strain parameters, showed that the phase transition is not strictly second order, with the critical exponent β ≠ 1/2. This study demonstrates the complex structural features of mixed cation metal oxides at elevated temperatures.

The magnetic modulation by the valence transition of polyoxometalate

Three novel vanadoborates with crown-shaped V12B32 cluster cages were successfully synthesized, differing only in their countercation. X-ray photoelectron spectroscopy (XPS) and Bond valence sum (BVS) analyses revealed distinct V4+/V5+ ratios (11:1, 10:2, and 10:2) in the cluster cage of the three compounds. Structural analyses indicated that the valence state ratio was modulated by the countercation. The magnetic properties of these compounds were examined using variable-temperature magnetic susceptibilities and two-dimensional correlation infrared spectroscopy (2D-COS-IR) under magnetic perturbation. This approach elucidated the origin and variability of their magnetic properties, demonstrating that the vanadium valence ratio and countercation significantly influence the magnetic behaviour of vanadoborates. The present study highlights the effectiveness of the transition of the vanadium valence state in the cluster cage by altering the countercation, providing a new avenue for the study of magnetically modulated materials.

Synthesis, structure and characterization of two new silver-iron based phosphates AgFe2(PO4)2F(H2O)2 and Ag3Fe2(PO4)(HPO4)3

Two new silver-iron based phosphates AgFe2(PO4)2F(H2O)2 (1) with monoclinic P21/n and Ag3Fe2(PO4)(HPO4)3 (2) with triclinic P-1 were synthesized by a conventional hydrothermal method, featuring a dimer structure and a twisted honeycomb-like lattice, respectively. XPS and BVS (Bond Valence Sum) calculations indicated only Fe3+ ions in both compounds, while FT-IR spectra proved the presence of [H2O] in 1 and [OH] groups in 2. Solid-state UV–vis–NIR diffuse reflectance spectra suggested their wide optical band gaps of 2.31 eV and 1.94 eV, respectively. Magnetic measurements indicated that both compounds display a long-range antiferromagnetic ordering at low temperature, showing the change of magnetic entropy of 9.59 J mol−1 K−1 in 1 and that of 14.87 J mol−1 K−1 in 2, respectively.

Investigation of optical and magnetic properties of 3d-4d transition metal ion based double Perovskite: Sr2MnRuO6

Investigation of physical properties in double perovskites, A2B′B″O6, containing 3d/4d transition metal ions at the B sites is an interesting avenue of research. In this study, we focus on Sr2MnRuO6, exploring its structural, morphological, optical and magnetic properties. Sr2MnRuO6 was synthesized in single phase using solid-state reaction route. It crystallizes in a tetragonal structure (space group I4/mcm, #140) with lattice parameters a = 5.4633 (2) Å, c = 7.9419 (1) Å. X-ray diffraction analysis revealed no super lattice reflections, indicating disorder in the B-site cations.The Jahn-Teller distortion in Mn-O6 octahedra,as revealed by XRD results, indicates a high spin state for the Mn3+ ion. The stoichiometric ratio of Sr: Mn: Ru (∼2:1:1), as determined by bond valence sum calculations and confirmed by energy dispersive x-ray spectroscopy agree well with the nominal composition of Sr2MnRuO6. Diffuse reflectance spectroscopy showed strong absorption throughout the visible region with a direct band gap of ∼3 eV, indicating Sr2MnRuO6 is a potential candidate for optical applications. Huge photoluminescence emission observed in the visible region is attributed to Mn3+ ions. The temperature dependence of molar susceptibility data indicates a paramagnetic to antiferromagnetic transition around 195 K. The possible super exchange paths for antiferromagnetic interaction are Ru5+- 4d3 (t2g3eg0) − O1 − Ru5+- 4d3 (t2g3eg0) along the z axis, or Ru5+- 4d3 (t2g3eg0) − O2 − Ru5+- 4d3 (t2g3eg0) in the xy-plane, with the angles between these orbitals being nearly 180°. At low temperatures under a 10,000 Oe field, spin glass type magnetic behaviour is observed. The effective magnetic moment (6.17 μB) obtained from the Curie-Weiss fit from 260 K to 290 K nearly matched with the theoretical resultant effective moment (6.24 μB) by considering Mn3+ ions in HS state and Ru5+ ions.Specific heat measurements revealed no long-range magnetic ordering down to 2 K, further suggesting the role of cationic disorder in the magnetic behaviour of Sr2MnRuO6.

An 1,4,7,10-tetraazacyclododecane-nickel complex functionalized polymolybdate acting as artificial oxidase in removing methylene blue

The reactive oxygen species (ROS), serving as a crucial biochemical reaction medium, is intricately involved in a myriad of physiological and pathological processes. The proper use of ROS can solve many practical problems, for example killing harmful microorganisms or cells, removing pollutants in water, etc. Therefore, the design and synthesis of artificial oxidase with catalytic activity in producing ROS become a hot research spot from bio-inorganic chemistry to catalytic industry. Herein, a cyclen-nickel complex functionalized polymolybdate, [Ni(cyclen)(H2O)2]2[(AsO)6(NiMo6O24)]·3H2O (abbreviated as NiAM, cyclen = 1,4,7,10-tetrazacyclododecane), which can acting as a catalyzed oxidase to generating ROS, has been structurally characterized by means of single-crystal X-ray diffraction (SXRD), elemental analyses, IR and UV–vis spectra, powder X-ray diffraction (PXRD), and bond valence sums (Σs) calculation. The NiAM's principal element, as revealed by SXRD, indicates that it is an ionic complex that composed by two [Ni(cyclen)(H2O)2]2+and one modified Anderson-type cluster [(AsO)6(NiMo6O24)]4–. Interestingly, NiAM possesses effective ability in catalyzing the ROS generation in aqueous solution. As a result, it can remove methylene blue (MB) dyes from the stable solution system.

Novel Trinuclear Copper(II) Complex: Crystal Structure at 100 K and Magnetic Properties of (R, S)-di[(6,7-dimethoxy-isoquinolin-1-yl)-(3,4-dimethoxy-phenyl)-methanolato]-tetra(2-hydroxybenzoato)-diaqua-tricopper dihydrate, [Cu3(C7H5O3)4(C20H20NO5)2(H2O)2]·2(H2O)

The crystal structure of [Cu3(C7H5O3)4(C20H20NO5)2(H2O)2]·2(H2O) (1) and analysis of temperature and field dependence of magnetic susceptibility is reported in this work. The structure of 1 is composed of trinuclear complex units and water molecules. The middle copper atom occupies the center of symmetry. N, O-bonded (6,7-dimethoxy-isoquinolin-1-yl)-(3,4-di­methoxy-phenyl)-methanolato ligands, 2-hydroxybenzoates with bridging carboxylic groups, and oxo-bridged water molecules connect the middle Cu(II) atom with the terminal copper atoms. Two 2-hydroxybenzoates coordinate the terminal copper atoms via one carboxylic oxygen and an O atom of the hydroxyl group. The analysis of copper coordination by bond-valence sum approach and relevant structural correlation is consistent with hexacoordinated Cu(II) centers. Cu···Cu separation is 3.0269(3) Å. The magnetism of 1 shows a strong ferromagnetic interaction between the neighboring metallic centers accompanied by very weak antiferromagnetic intermolecular interactions. The complex units are mutually held by π···π stack interactions of 2-hydroxybenzoates and hydrogen bonds.Graphical A new N,O bonded ligands, (R, S)-[(6,7-dimethoxy-isoquinolin-1-yl)-(3,4-dimethoxy-phenyl)-methanolate] coordinate the terminal atoms of the trinuclear copper(II) complex.

Study on the electronics and structural properties of transition metal-doped La2Mo2O9.

La2Mo2O9 is a potential electrolyte material for SOFC due to its higher oxygen conduction at high temperatures. However, La2Mo2O9 suffers from detrimental phase transition at high temperature from monoclinic α to cubic β phase. This phase transition can be prevented by lowering the temperature. However, lowering the temperature reduces the ionic conductivity. Substitution of transition metal on Mo site is the best strategy for the suppression of phase transition. In the present work, the effect of substituting element on different sites has been investigated. From the result, it is observed that the band gap increases with concentration of Er. For the assessment of mechanism behind the improved performance, the atomic insight is crucial. For that, we have employed ab initio DFT calculation. We have used PBE and grimme d3 dispersion correction for the accuracy of evaluated band gap and electrochemical stability. All DFT calculations have been performed using Quantum ESPRESSO pwscf code's and for the assessment of thermodynamical stability of La2Mo2O9 and the doped structures, an alternative descriptor, the global instability index (GII), which is based on the bond valance sum approach implemented in SoftBV was used. All the visualizations were done by XCrySDen and VESTA open source software.

Ho2Zr(MoO4)5 — A novel double molybdate with negative thermal expansion

In this study we investigated the subsolidus phase equilibria in the Ho2O3–ZrO2–MoO3 system and discovered the double molybdate Ho2Zr(MoO4)5. The Rietveld method was used to refine the structures of the low- and high-temperature phases. The title compound is isostructural to Er2Zr(MoO4)5 double molybdate and crystallizes in the monoclinic space group P21, but rearranges to rhombic (space group Cmc21) at temperatures above 100°С. Ho2Zr(MoO4)5 exhibits negative thermal expansion in the high temperature region (αV = −3.9 × 10−6 °C−1). Theoretical calculations using bond valence sum maps method suggest that this compound may have three-dimensional O2− conductivity with relatively low energy barriers (0.588 eV).

Structural, morphological, electrical, and dielectric properties of Na2Cu5(Si2O7)2 for ASSIBs.

Solid inorganic electrolyte materials are fundamental components for constructing all-solid-state sodium-ion batteries. These solid electrolytes offer considerable benefits related to safety, electrochemical performance, and mechanical stability in comparison to liquid organic electrolyte systems. This study investigates the sodium ion conduction mechanism and relaxation kinetics in the sorosilicate material Na2Cu5(Si2O7)2, a potential solid electrolyte, using impedance spectroscopy. Analysis of the DC conductivity data demonstrates that sodium ion mobility follows Arrhenius behavior with a thermal activation energy barrier of 1.21 eV. This work highlights the importance of carefully choosing an appropriate equivalent circuit model to extract DC conductivity parameters from impedance data, given the contributions from both grain and grain boundary effects. Analysis of the AC conductivity and dielectric constant as a function of frequency and temperature demonstrates that ionic conduction takes place in this material through a process in which charge carriers overcome correlated energy barriers, known as correlated barrier hopping. The neutron diffraction patterns were analyzed using soft bond valence sum (BVS) techniques to map the possible ionic conduction pathways within the unit cell. Examination of the data points to obstructions in the sodium ion diffusion routes along the a-axis and diagonal of the bc plane within the triclinic unit cell. These bottlenecks likely contribute to the high activation energy and correspondingly low ionic conductivity observed. Analysis of dielectric properties by modulus verified that the ionic conduction relaxation phenomena exhibit thermal activation and a distribution of relaxation times. In summary, this work elucidates the microscopic ionic conduction mechanism in Na2Cu5(Si2O7)2 through extensive analysis encompassing DC/AC conductivity, electric modulus, and dielectric constant measurements. The insights gained into the ionic conduction mechanism will aid in engineering optimized ionic conductor materials for battery technologies.

Synthesis, crystal structure and investigation of ion-exchange possibility for sodium tellurate NaTeO3(OH).

A new sodium tellurate has been hydrothermally synthesized and comprehensively analysed using spectroscopic and thermogravimetric techniques, resulting in the determination of its composition as NaTeO3(OH). The analysis of synchrotron X-ray and neutron diffraction data indicates that NaTeO3(OH) has a crystal structure similar to that of the previously reported tellurate, KTeO3(OH), with the space group P21/a (No. 14). NaTeO3(OH) consists of zigzag one-dimensional chains built by edge-sharing TeO6 octahedra, running parallel to the c-axis and connected to sodium and hydrogen atoms. The hydrogen atoms covalently bond to the terminal oxygen atoms on the one-dimensional chain and also form hydrogen bonds with other terminal oxygen atoms on nearby chains. The structure has been confirmed by optimization using the pseudopotential method and performing Bond Valence Sum (BVS) analysis. Although Li+ ions in LiTeO3(OH) can be exchanged reversibly with H+ ions, no ion exchange behaviour is observed in NaTeO3(OH). The difference is attributed to the size of the alkali ions and their crystal structure.

Structural Analysis, Characterization, and First-Principles Calculations of Bismuth Tellurium Oxides, Bi6Te2O15

A single crystal of Bi6Te2O15 was obtained from the melt of the solid-state reaction of Bi2O3 and TeO3. Bi6Te2O15 crystallizes in the Pnma space group (No. 62) and exhibits a three-dimensional network structure with a =10.5831(12) Å, b = 22.694(3) Å, c = 5.3843(6) Å, α = β = γ = 90°, V = 1293.2(3) Å3, and Z = 4. The structure was determined using single-crystal X-ray diffraction. An asymmetric unit in the unit cell, Bi3Te1O7.5, uniquely composed of four Bi3+ sites, one Te6+ site, and nine O2− sites, was solved and refined. As a bulk phase, Bi6Te2O15 was also synthesized and characterized using powder X-ray diffraction (XRD), infrared (FT-IR) spectrometry, and the thermogravimetric analysis (TGA) method. Through bond valence sum (BVS) calculations from the single crystal structure, Bi and Te cations have +3 and +6 oxidation numbers, respectively. Each Bi3+ cation forms a square pyramidal structure with five O2− anions, and a single Te6+ cation forms a six-coordinated octahedral structure with O2− anions. Since the lone-pair electron (Lp) of the square pyramidal structure, [BiO5]7−, where the Bi+ cation occupies the center of the square base plane, exists in the opposite direction of the square plane, the asymmetric environments of all four Bi3+ cations were analyzed and explored by determining the local dipole moments. In addition, to determine the extent of bond strain and distortion in the unit cell, which is attributed to the asymmetric environments of the Bi3+ and Te6+ cations in Bi6Te2O15, bond strain index (BSI) and global instability index (GII) were also calculated. We also investigated the structural, electronic, and optical properties of the structure of Bi6Te2O15 using the full potential linear augmented plane wave (FP-LAPW) method and the density functional theory (DFT) with WIEN2k code. In order to study the ground state properties of Bi6Te2O15, the theoretical total energies were calculated as a function of reduced volumes and then fitted with the Birch–Murnaghan equation of state (EOS). The band gap energy within the modified Becke–Johnson potential with Tran–Blaha parameterization (TB-mBJ) revealed a value of 3.36 eV, which was higher than the experimental value of 3.29 eV. To explore the optical properties of Bi6Te2O15, the real and imaginary parts of the dielectric function, refraction index, optical absorption coefficient, reflectivity, the real part of the optical conductivity extinction function, and the energy loss function were also calculated.

Tartrate bridging ligands in divalent Co(II)/Co(III) dinuclear anion

A cobalt(II/III) ionic compound with bridging tartaric acid (H4L) anion (CH6N3)3[Co2II/III(L)2(H2O)2]·4H2O 1 was synthesized. The crystallites were isolated from highly alkaline aqueous solution in the presence of guanidinium cations (CH6N3)+ being then incorporated as counter ions.A determined structure reveals the dinuclear coordination anion with two cobalt centers, each within its distinctive coordination octahedron CoO6 sphere showing different Co−O bond lengths. The metal center with shorter coordination bonds is assigned as Co(III), while the other with Co(II), all in agreement with overall net charge equilibrium. This involves three guanidinium cations, two tartrate(4-) anions, the latter within the coordination anion, as well as with bond valence sums for both cobalt centers. Both tartrates (L) are triply bonded on the Co(III) center, thus enabling CoIIIO6 coordination bonds. On the other hand, only two coordination bonds are enabled by each tartrate towards Co(II), while the remaining two in CoIIO6 are completed by two terminal water molecules. The electronic spectrum shows clearly the d-d bands at 400 and 665 nm for Co(III), while at 520 nm for Co(II), for each CoO6, respectively. The temperature dependent magnetic susceptibility shows the paramagnetic behavior of the compound, due to the d7 Co(II) ions being in a high spin state, while the d6 low spin Co(III) ions are diamagnetic.

Hydrothermal assembly strategy for the construction of oxygen‐bridging lanthanide‐substituted bilacunary Keggin‐type germanotungstate tetramers encapsulating [W3O12]6− connector

AbstractUnder the hydrothermal condition and presence of organic amines, incorporating lanthanide (Ln) ions into monolacunary Keggin‐type germanotungstate precursor resulted in the formation of two new complex clusters formulated as H17(H2en)5[K3(H2O)(GeW10O37TbOTb)4(μ6‐W3O12)] ⋅ 45H2O (GeW‐Tb) and H22(H2en)3[K2(GeW10O37EuOEu)4(H2O)(μ6‐W3O12)] ⋅ 44H2O (GeW‐Eu) (en=ethylenediamine), which have been structurally characterized by elemental analyses, ICP analysis, IR spectra, thermogravimetric analysis, bond valence sum calculations and single‐crystal X‐ray diffraction. The most prominent structural feature of GeW‐Eu and GeW‐Tb revealed an unprecedented oxygen‐bridging Ln‐substituted bilacunary Keggin‐type germanotungstate tetramers encapsulating [W3O12]6− connector. What's more interesting is that a versatile library of linkable units including bilacunary germanotungstate [α‐GeW10O37]10−, internal oxo group between two Ln ions, as well as central tritungstate intermediate [W3O12]6− are all generated in situ thanks to the potential promotion of hydrothermal reaction system. In particular, the possible assembly mechanism for the complex clusters is proposed, and their solid‐state photoluminescence properties are also discussed in detail. To our knowledge, both [α‐GeW10O37]10− and [W3O12]6− intermediates are the highly robust POM building blocks that were first discovered. The studies highlight the structural diversity of Ln‐substituted germanotungstates and provide a new direction in the design of other functional germanotungstate based POMs in the future.

A Machine Learning Study on High Thermal Conductivity Assisted to Discover Chalcogenides with Balanced Infrared Nonlinear Optical Performance.

Exploration of novel nonlinear optical (NLO) chalcogenides with high laser-induced damage thresholds (LIDT) is critical for mid-infrared (mid-IR) solid-state laser applications. High lattice thermal conductivity (κL ) is crucial to increasing LIDT yet often neglected in the search for NLO crystals due to lack of accurate κL data. A machine learning (ML) approach to predict κL for over 6000 chalcogenides is hereby proposed. Combining ML-generated κL data and first-principles calculation, a high-throughput screening route is initiated, and ten new potential mid-IR NLO chalcogenides with optimal bandgap, NLO coefficients, and thermal conductivity are discovered, in which Li2 SiS3 and AlZnGaS4 are highlighted. Big-data analysis on structural chemistry proves that the chalcogenides having dense and simple lattice structures with low anisotropy, light atoms, and strong covalent bonds are likely to possess higher κL . The four-coordinated motifs in which central cations show the bond valence sum of +2 to +3 and are from IIIA, IVA, VA, and IIB groups, such as those in diamond-like defect-chalcopyrite chalcogenides, are preferred to fulfill the desired structural chemistry conditions for balanced NLO and thermal properties. This work provides not only an efficient strategy but also interpretable research directions in the search for NLO crystals with high thermal conductivity.

Synthesis, structural study, and Na+ migration pathways simulation of the new phase Na3Al3(AsO4)4

Single crystals of the novel arsenate, Na3Al3(AsO4)4 have been isolated and their structure has been determined by X-ray diffraction experiment. Na3Al3(AsO4)4 crystallizes in the monoclinic space group C2/c with a = 19.837(1) Å; b = 6.448(3) Å; c = 10.437(6) Å, β = 91.986 (3)° and Z = 2. The structural model was confirmed by both bond valence sum (BVS), charge distribution (CHARDI) validation tools and density functional theory (DFT) method. The empirical activation energy for sodium migration channels within the crystal structure was estimated by the bond valence site energy landscape (BVSE) map method. With an energy barrier of 0.409 eV, the crystal structure features 3D networks of pathways suitable for Na+ ion migration.