Search

Photodetectors based on lead halide perovskites often show excellent performance but poor stability. Herein, we demonstrate a photodetector based on MAPbBr3 single crystals passivated with an ultrathin layer of PbSO4, which shows superior detectivity and on/off ratios compared to the control device due to the combined effect of lower surface traps, reduced recombination and low dark current. In addition, the device retained ∼56% of its initial D* with an impressive on/off ratio of ∼801 after one year compared to ∼22% of D* and an on/off ratio of ∼6 of the control device. [ABSTRACT FROM AUTHOR]

"CrystEngComm" is a journal focused on solid-state and crystalline materials, published by The Royal Society of Chemistry. The latest issue includes articles on topics such as gas hydrate growth mechanisms, thermochromic-to-photochromic conversion, and solvent-induced structural changes in macrocyclic arenes. The journal covers a wide range of interdisciplinary features and innovative material innovations in industrial chemistry. [Extracted from the article]

Pr-doped 0.70Pb(Mg1/3Nb2/3)O3–0.30PbTiO3 (PMNT:Pr) single crystals are grown with the seed-guided Bridgman method. The PMNT:Pr crystal remains a pure perovskite structure with Pr3+ ion doping. The maximum d33 of the morphotropic phase boundary is 2636 pC N−1 at 10 Hz, 20 cycles and 14 kV cm−1. The dielectric constant is higher than 4300 at room temperature and 0.1 kHz. The coercivity field Ec and remaining polarization Pr decrease with increasing temperature at 10 kV cm−1 and 10 Hz, respectively. The ferroelectric domains become periodically dense and regular, and the domain size is uniform under the AC polarization. In the wavelength range of 200–2000 nm, the transmittance of the crystal under the non-polar mode, DC-polar mode and AC-polar mode is 29–37%, 33–51% and 53–61%, respectively. The crystal excitation at 451 nm yielded the strongest red light emission at 651 nm, and the luminescence intensity decreased with increasing temperature. PMNT:Pr single crystals have been proved to be rare-earth doped ferroelectric single crystal materials with high piezoelectric properties. [ABSTRACT FROM AUTHOR]

Hybrid halide perovskites form a promising class of light-absorbing materials. Among the numerous 3D semiconducting perovskites, there is a group of emerging aziridinium-based hybrids that are considered to be prospective materials for optoelectronic applications. In this work, we report the mixed halide aziridinium perovskites of (AzrH)PbBrxI3−x series (AzrH = aziridinium). Small changes in the composition of perovskites are shown to have a defining impact on the optoelectronic properties of the reported materials. Halogen substitution allowed a variation in band gap values of these compounds, ranging from 1.57 to 2.23 eV, as established using electronic spectroscopy. Crystal structures of (AzrH)PbBrxI3−x perovskites were studied using single crystal and powder X-ray diffraction analysis. The lattice constant had a linear dependence on the Br content in the structure, thus strictly following Vegards's law. Importantly, the reported compounds displayed a preferential inclusion of iodine upon synthesis, revealing that the mixed halide perovskite composition cannot be estimated based on the precursors' ratio only, and it should be post-synthetically checked. The reported results expand the range of hybrid perovskites with tuneable band gaps beyond the conventional methylammonium and formamidinium-based perovskites and offer a new series of metal-halide hybrids suitable for photovoltaic and other optoelectronic applications. [ABSTRACT FROM AUTHOR]

Quasi-2D DJ type perovskites theoretically offer excellent properties for X-ray detection, but they often face issues such as phase segregation and small crystal size. In this study, we synthesized large single crystals of quasi-2D DJ type perovskite (3AMPY)(MA)Pb2Br7 using temperature-controlled crystallization. The resulting X-ray detector exhibited high resistivity (1.78 × 109 Ω cm), a carrier mobility–lifetime (μτ) product of 9.32 × 10−4 cm2 V−1, a dark current of 5.6 × 10−8 A cm−2 V−1, and a sensitivity of 129.86 μC Gy−1 cm−2. These results demonstrate the potential of quasi-2D DJ type perovskites for high-performance X-ray detection and provide insights into improving crystal growth for optoelectronic applications. [ABSTRACT FROM AUTHOR]

In this paper, we present the synthesis and characterization of a rubidium vanadium(III) vanadyl(IV) phosphate, obtained under hydrothermal conditions. The new compound crystallizes in the triclinic space group P1 with the unit cell parameters a = 9.637(1), b = 12.254(2), c = 12.336(2) Å, a = 105.82(1), ß = 104.81(1) and γ = 102.75(1)°. Its crystal structure was determined by single crystal X-ray diffraction. The structure of Rb3V3+(V4+O)(PO4)(H0.5PO4)2 is formed from V3+-centered octahedra sharing all oxygen vertices and one edge with phosphate tetrahedra to form ribbons parallel to the [011] direction. These ribbons are further linked via V4+O5 polyhedra in a three-periodic framework with channels running parallel to the a and b axes. Rb atoms occupy positions inside the framework channels. The title compound achieves a long range ordered antiferromagnetic state at TN = 2.1 K and formally demonstrates a high value of the magnetic frustration parameter f equal to the ratio of the Weiss and Néel temperatures |T|/TN = 15, which can be attributed to the reduced dimensionality of the magnetic subsystem. At T < TN, the magnetization curve exhibits the signature of the 1/3 plateau. [ABSTRACT FROM AUTHOR]

In this contribution we are introducing a Variable Bridging Ligand (VBL) strategy for the preparation of heterometallic complexes. One synthetic challenge associated with other methods described in the existing literature stems from the fact that if there is a need to change the donor groups on a metalloligand, both the initial ligand and the resulting metalloligand must be synthesized all over again. To circumvent this problem, we reasoned that if a metal complex would have one labile ligand that can be easily replaced by various bridging polytopic species, several metalloligands can thus be generated starting from the same starting material. Experimentally, we describe here the synthesis and characterization of a new ligand, bis(pyrazol-1-yl)-N-(quinolin-8-yl)acetamide, HLQ2Pz (Pz = pyrazolyl ring) and its reactions with copper(II) centers. In a first step, pro-metalloligand preparation was investigated using Cu(II) primary metallic centers and the HLQ2Pz main ligand to produce (LQ2Pz)Cu(OAc)·H2O, (LQ2Pz)Cu(BF4), and (LQ2Pz)Cu(ClO4)·MeCN complexes. Using (LQ2Pz)Cu(ClO4)·MeCN as a pro-metalloligand, two metalloligands (LQ2Pz)Cu[O2CCH(pz)2] and (LQ2Pz)Cu[O2CCH(CH2pz)2] were prepared. Employing the latter metalloligand, two mixed valence CuII/CuI complexes, {(LQ2Pz)CuII[O2CCH(CH2pz)2CuI(PPh3)2]}NO3 and {(LQ2Pz)CuII[O2CCH(CH2pz)2]}2CuI(PF6) were synthesized. These compounds were characterized by NMR, UV-Vis, and IR spectroscopy, and in solid state by single crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

This publication describes monodentate phosphine and oxazoline ligands attached to an amino acid ester and the application of their supramolecularly assembled rhodium(I) or iridium(I) complexes in asymmetric catalysis. The major feature of these complexes is the transmission of chirality from distant hydrogen bonded amino acids to the prochiral catalytic metal center ("backdoor induction"). The in situ generated homoleptic and heteroleptic rhodium(I) or iridium(I) precatalysts were studied by NMR, UV-VIS and CD spectroscopy as well as X-ray single crystal diffraction. In asymmetric hydrogenation of methyl a-acetamidocinnamate, rhodium(I) and iridium(I) complexes afforded complete conversions with enantioselectivities up to 85%, while iridium complexes proved to be more sensitive to the variation of reaction conditions, including catalyst loading, metal to ligand ratio and temperature. The hydrogenation of four other dehydroamino acid substrates resulted in similar conversion and selectivity as obtained with methyl a-acetamidocinnamate. The influence of the phosphine/oxazoline heteroleptic mixtures in catalysis was studied using both rhodium(I) and iridium(I) complexes. Finally, a homoleptic phosphine rhodium(I) complex was successfully applied in asymmetric hydroformylation of styrene and 1-octene with complete conversions and selectivity up to 40% ee for the branched styrene product. [ABSTRACT FROM AUTHOR]

Propranolol is a popular active pharmaceutical ingredient (API), a competitive non-cardioselective sympatholytic beta blocker, listed in the WHO Model List of Essential Medicines. Although, since its invention in 1962, multiple salts and cocrystals of propranolol have been obtained, in most of the commercially available drugs it exists in a form of racemic hydrochloride. Inconsistency exists in the previously deposited crystal structures of this salt, with some of them indicating structural disorder. Therefore, in this work the single crystal X-ray diffraction, solid state NMR and CASTEP periodic DFT calculations were combined to explain this phenomenon and characterize the crystal structure of this API. The obtained results clearly indicate the presence of static disorder in the crystal structure, pointing the most favorable arrangements. Besides, the comparison with the results obtained for the structures of pure enantiomers explained why the studied API forms racemic systems instead of complete chiral discrimination in the solid state. [ABSTRACT FROM AUTHOR]

Bi12TiO20–BaTiO3 bulk composite ceramics prepared by sintering a mixture of presynthesized BaTiO3 and Bi12TiO20 particles around the melting point of Bi12TiO20 could exhibit direct as well as inverse piezoelectricity without electrical polarization. To prevent the permeation of melting Bi12TiO20 into a substrate and thus increase the composition gradient, samples were sintered on an Al2O3 (0001) single crystal substrate instead of an Al2O3 ceramic substrate. In this study, the Al2O3 single crystal substrate sintering method was surprisingly found to be an effective method to improve the piezoelectric performance of Bi12TiO20–BaTiO3 ceramics. These samples showed an enhanced piezoelectric strain coefficient (d33) by 80% compared to samples sintered on Al2O3 ceramics. Moreover, the d33 value remains nearly identical over the entire surface. Combining the results of XRD, EDS, XPS, ICP and Raman spectroscopy, the improved piezoelectricity might be because of the alignment of distorted BiO5 polyhedra in the amorphous Bi12TiO20 phase caused by the composition gradient. These results offer a method to enhance the piezoelectric properties of Bi12TiO20-based ceramics and will inspire further research to develop Bi12TiO20-based ceramics suitable for practical use. [ABSTRACT FROM AUTHOR]

We report the synthesis and characterization (Raman, FTIR, DLS, single crystal XRD) of Cs10H3SbW14O50·6H2O, which contains a new polyoxometalate building block: H3SbW14O5010− (SbW14). Solution-state fluorescence, DLS, and UV-vis absorbance results with Nd3+, Eu3+, Am3+, and Cm3+ confirm that SbW14 acts as an efficient complexant and fluorescence sensitizer for f-elements. [ABSTRACT FROM AUTHOR]

This study introduces a rapid and non-destructive impurity characterization method using UV absorption spectroscopy that is calibrated against secondary ion mass spectrometry (SIMS) data. A random forest regression model was evaluated for carbon, oxygen, and silicon impurity prediction based on absorption spectra. AlN boules were grown using the seeded PVT method with tungsten crucibles, processed into wafers, and characterized. A matrix of 37 samples with varying impurity concentrations in the range 1 × 1017 to 5 × 1019 cm−3 was created using element-specific doping methods. SIMS and absorption spectroscopy data revealed characteristic absorption patterns for different impurities. Absorption at 230 nm, which is a crucial wavelength for UVC-LEDs, correlated well with the overall impurity concentration. The random forest model predicted impurity concentrations accurately when similar training data were available, but high prediction errors occurred for unique impurity profiles. To improve prediction accuracy, a more extensive sample series and/or more complex AI tools are required. [ABSTRACT FROM AUTHOR]

In this contribution, a series of copper(II) discrete and polymeric coordination compounds, namely [Cu3L2(aze)2]n·nH2O (1·nH2O), [CuL2]·H2O (2·H2O) and [CuL(H2O)(Haze)]·H2O (3·H2O) were fabricated from (pyridin-2-yl)methylenenicotinohydrazide (HL) and azelaic acid (H2aze), using evaporative crystallization, grinding and slurry synthesis methods. The solvent crystallization method produced a crystalline precipitate of complex 1·nH2O. The filtrate allowed the production of crystals of complex 3·H2O. The grinding synthetic method gave rise to a mixture of complexes 1·nH2O, 2·H2O and an undetermined phase. Results of the slurry synthetic approach highly depend on the stirring time. The obtained coordination compounds have been fully characterized by single crystal X-ray diffraction revealing different structures of complexes, viz. from mononuclear homo- and heteroleptic complexes (2 and 3) to a 1D heteroleptic coordination polymer (1). DFT calculations on non-polymeric complexes were conducted to evaluate the hydrogen-bonding and π-stacking interactions that play a critical role in the solid-state structures of complexes 2 and 3. Additionally, the impact of co-crystallized water molecules, which enhance the π-stacking interactions, was analyzed using energy decomposition analysis. [ABSTRACT FROM AUTHOR]

With the type, size and quality of experimental samples playing a special role in searching for new materials, single crystal samples are of high value and methods of their fabrication have to be developed and constantly improved, to be adjusted to the peculiarities of an expected compound. The flux technique for producing chromium-containing materials is characterized by the low solubility of Cr2O3 used. The study deals with crystallization of Cr-containing borates HoCr3(BO3)4 with a huntite structure and oxyborates Cu2CrBO5 with a ludwigite structure in flux systems based on Li2WO4. Consideration is given not only to the possibility of growing sizable single crystals of these compounds, but also to a mixed huntite–ludwigite flux system intended to unify the growth technology and to identify the phase boundary of these compounds. The investigation of the phase diagram allowed the secondary phases to be found and analyzed. Powder and single crystal X-ray diffraction and element-sensitive EDX techniques were used to control the composition and structure of the obtained compounds. Orientational thermal and field dependences of magnetization of the obtained crystals HoCr3(BO3)4 and Cu2CrBO5 were measured. [ABSTRACT FROM AUTHOR]

Two new rhenium(I) tricarbonyl complexes of general formula [Re(CO)3(L1/L2)] (1/2) were fabricated and thoroughly characterized by diverse spectroscopic techniques. The crystal structures of the complexes were confirmed by single crystal X-ray diffraction, which disclosed distorted octahedral geometry around the central metal. A theoretical calculations by DFT and TDDFT were carried out to support experimental observations. The DNA-binding ability of complexes with calf thymus DNA was investigated by UV-Vis absorption and fluorescence spectroscopy. Viscosity studies suggested an intercalative mode of binding of the complexes with CT-DNA. BSA protein-binding studies revealed quenching of tryptophan and tyrosine residues in the presence of complexes, and the quenching mechanism was shown to be static. Changes in the microenvironmental and structural properties of BSA were scrutinised by circular dichroism, synchronous and 3D fluorescence studies. The in vitro toxicity of the complexes against a human-breast epithelial adenocarcinoma cell line (MCF-7) and human-breast epithelial cell line (used as normal cell line; MCF-10A) was explored using the MTT assay. [ABSTRACT FROM AUTHOR]

We report binuclear arene Ru(II) benzhydrazine complex catalysed eco-friendly, selective and sustainable synthesis of bioactive pyrimidinones via acceptorless dehydrogenative annulation of alcohols. Facile synthesis of three new binuclear ruthenium(II) complexes of general formula [(η6-p-cymene)2Ru2(L)Cl2] (BC1–BC3) (where L = biphenyl benzhydrazine derivatives) has been accomplished by the reaction of [(η6-p-cymene)2Ru2Cl2(μ-Cl)2] with biphenyl hydrazine ligands (BL1–BL3). The formation of the newly synthesized ruthenium complexes has been authenticated by analytical and spectral (FT-IR, UV-vis, NMR and HR-MS) techniques. The three-dimensional molecular architecture of one of the representative complexes (BC3) has been ascertained by single crystal XRD study, which revealed the presence of a pseudo octahedral geometry around ruthenium. Furthermore, the catalytic activity of all the complexes has been examined towards the construction of substituted pyrimidinones from the coupling of readily available alcohols, ethyl cyanoacetate and amidine hydrochlorides using acceptorless dehydrogenative annulation (ADA) methodology. A library of 6-oxo-1,6-dihydropyrimidine-5-carbonitrile derivatives (20 examples) has been synthesised using 1 mol% of ruthenium catalyst (BC2) loading with a maximum yield of up to 92% and H2, H2O and ethanol as the only by-products. The utility of the existing catalytic protocol has been extended to a large-scale synthesis of one of the derivatives 6-oxo-1,6-dihydropyrimidine-5-carbonitrile in 73% isolated yield. Furthermore, anticancer drug "bropirimine" has been successfully achieved by utilizing the current catalytic protocol. [ABSTRACT FROM AUTHOR]

We have synthesized four new oxygen/sulfur(O^S) chelate complexes, [Zn(L)2], where L represents different ligands: methyl-3-hydroxy-3-(furyl)-2-propenedithioate (L1, 1), methyl-3-hydroxy-3-(p-fluorophenyl)-2-propenedithioate (L2, 2), methyl-3-hydroxy-3-(p-chlorophenyl)-2-propenedithioate (L3, 3), and methyl-3-hydroxy-3-(p-bromophenyl)-2-propenedithioate (L4, 4). These complexes have been characterized by using IR, multinuclear NMR (1H, 13C{1H}, and 19F{1H}), and UV-vis spectroscopy. The structural characterization of complexes 1, 2, and 4 was further achieved by single crystal X-ray diffraction (SCXRD). The supramolecular structures of these complexes are stabilized by non-covalent C–H⋯π (ZnOSC3, chelate), C–S⋯π (ZnOSC3, chelate), π⋯π (ZnOSC3,), C–H⋯O, C–H⋯F–C and C–H⋯H–C interactions. The luminescence properties of Zn(II) complexes 1–4 were studied at room temperature in the solid phase. The antileishmanial activity was evaluated for all complexes. Complexes 1 and 4 exhibited significant anti-promastigote and anti-amastigote activities, with IC50 values of 2.0 and 1.33 μg mL−1, and 2.79 and 2.02 μg mL−1, respectively. Additionally, cytotoxicity assays demonstrated that these Zn(II) β-oxodithioester complexes were toxic to promastigotes, but showed reduced toxicity towards RAW 264.7 cell lines at varying concentrations. Furthermore, the optical band gap energies of complexes 1–4 were measured and found to exhibit semiconducting behavior. [ABSTRACT FROM AUTHOR]

Photocyclization of 8-aryloxy-3-phenylbenzo[e][1,2,4]triazines leads to π-delocalized helicene radicals 1[n] (n = 5, 6, 7) containing the ring-fused 1,4-dihydro[1,2,4]triazin-4-yl as a spin source. Single crystal XRD revealed that the photocyclization to 1[n] involves a Smiles rearrangement. Radicals 1[n] were investigated by spectroscopic, electrochemical and DFT methods, while racemic helicene 1[7] was resolved and ECD spectra were recorded. [ABSTRACT FROM AUTHOR]

The document is a contents list from the journal CrystEngComm, focusing on the design and understanding of solid-state and crystalline materials. It includes papers on topics such as bio-templated synthesis, dynamic manipulation of luminescence, and the formation of hybrid capacitors. The journal is published by The Royal Society of Chemistry and features a range of research articles in the field of chemistry. [Extracted from the article]

Environmental-friendly alternatives to the commercial scintillator CdWO4, which contains the toxic element Cd, are highly desired. As potential candidates, in this work, the scintillation characteristics of Nb:YTaO4 transparent single-crystals grown from melt by the floating-zone technique are studied. It is found that the broad UV luminescence of YTaO4 can be turned into a broad visible one by the partial substitution of Ta with only 2% Nb. Therefore, Nb incorporation promotes a better spectral matching to Si-photodiode detectors while the high stopping power of YTaO4 is kept, being close to that of commercial CdWO4. The scintillation properties of pure YTaO4, with a light yield of 15 900 ph MeV−1 and an afterglow of 0.008% after 40 ms, are comparable to those of CdWO4. The light yield weighed with a Si-photodiode reaches maximum values for 0.5 & 1% Nb:YTaO4 crystals. An improvement in optical properties is expected by the growth of higher quality crystals by a flux-technique in the future. [ABSTRACT FROM AUTHOR]

Four new triphenylphosphine-derived cage ligands were modularly synthesized via dynamic imine chemistry (DIC), and their absolute structures were characterized by single crystal X-ray diffraction (SXRD), nuclear magnetic resonance (NMR) and high resolution mass spectroscopy (HRMS). In contrast to smallmolecule analogues, cage ligands demonstrate superior activity and selectivity. The Rh/Cage-L2 catalyst exhibits remarkable performance with an aldehyde selectivity of 89%, accompanied by a TOF value of 2665 h−1 and an l/b ratio of 2.60, thereby showcasing leading activity, chemical selectivity, and regioselectivity in the realm of homogeneous catalysts that rely on triphenylphosphine ligands. The reason for the formation of a higher l/b ratio, with a 3.84 kJ mol−1 difference in the energy of the rate-determining step, has been explained through density functional theory (DFT) calculations. In addition, a Janus-type PPh3-Au complex has been discovered during the study of the coordination of cage ligands, offering partial corroboration for the single coordination mechanism of these cage ligands. The large steric hindrance effect of cage ligands is believed to play a pivotal role in the hydroformylation reaction. This work highlights the potential application of cage ligands and inspires future efforts in the search of highly selective and efficient organometallic catalysts. [ABSTRACT FROM AUTHOR]

We have synthesized the first hydrous sp³-carbonate by laser-heating Ba[CO3], CO2 and H2O in a diamond anvil cell at 40(3) GPa. The crystal structure of Ba[H4C4O10][H3C4O10][H2CO3][HCO3] was determined by synchrotron single crystal X-ray diffraction. The experiments were complemented by DFT-based calculations. This compound is the first example of a carbonate containing both trigonally-coordinated carbon in [CO3]2−-groups and tetrahedrally coordinated carbon in [CO4]4−-groups. The [CO4]4−-groups polymerize by corner-sharing to form pyramidal [C4O10]4−-groups, which can bind three or four hydrogen atoms. As the pyramidal [C4O10]4−-groups are a constituent of several anhydrous sp³-carbonates, we now expect that further high-pressure hydrous carbonates can be obtained. [ABSTRACT FROM AUTHOR]

We have successfully synthesized bulk single crystals of S0.66(2)WS2 using a topochemical method, confirming the successful intercalation of sulfur into the interlayer space of M-WS2, which induces hole doping. The material exhibits superconductivity with a transition temperature of 6.5 K, making it the first anion-intercalated/hole-doped TMD material. This innovative approach to achieving hole doping through anion intercalation offers significant potential for application to other TMDs, enabling better control over their properties and potentially uncovering new quantum phenomena. This work marks a major step forward in the exploration and modulation of TMD-based materials. [ABSTRACT FROM AUTHOR]

Heating a single crystal of carbamazepine (III) (the thermodynamically stable form) in contact with solid palmitic acid resulted in the melting of palmitic acid and the growth of the crystals of carbamazepine (II) (the least stable polymorph) at the interface "carbamazepine (III) crystal–palmitic acid melt". The study suggests a possible mechanism of the transformation of carbamazepine (III) into carbamazepine (II) on mechanical treatment with palmitic acid as an additive. [ABSTRACT FROM AUTHOR]

Three new tertiary phosphane-appended heteroleptic Ni(II)-dithiolates with the formula [Ni(CAM)(dppe)] (Ni-1), [Ni(CAM)(dppf)] (Ni-2) and [Ni(CAM)(PPh3)2] (Ni-3) (CAM = cyanoacetamide dithiolate; dppe = 1,2-bis-(diphenylphosphinoethane); dppf = 1,1′-bis-(diphenylphosphino)ferrocene and PPh3 = triphenylphosphane) have been synthesized and characterized spectroscopically and using single crystal X-ray diffraction technique. The single crystal X-ray analysis of Ni-1, Ni-2 and Ni-3 reveal distorted square planar geometry around Ni(II), wherein Ni(II) is coordinated to the two sulfur centres of a CAM ligand in the bidentate chelating mode and two phosphorus centers of dppe, dppf and PPh3 ligands. Solid-state frameworks in these complexes are stabilized by C–O⋯H, C–N⋯H, C–S⋯H and C–H⋯C non-covalent intermolecular interactions. Ni-2 exhibits intramolecular (Ar)C–H⋯Ni anagostic interaction, which is absent in Ni-1 and Ni-3. Ni-3 exhibits intramolecular π⋯π stacking between the phenyl rings. The nature of these interactions have been assessed using Hirshfeld surface analyses, density functional theory (DFT) and quantum theory of atoms-in-molecules (QTAIM) calculations. Furthermore, the complexes have been employed as a homogeneous electrocatalyst for electrochemical hydrogen evolution reactions (HERs) using trifluoroacetic acid (TFA) as the hydrogen source. Electrochemical studies reveal turnover frequency (TOF) values of 319, 341 and 543 s−1 for Ni-1, Ni-2 and Ni-3, respectively, at 50 mM concentration of TFA. The plausible reason for the relatively better electrocatalytic activity of Ni-3 is ascribed to the coordination flexibility of the PPh3 ligand and the relatively larger positive natural charge over the nickel center and smaller HOMO–LUMO energy gap. [ABSTRACT FROM AUTHOR]

We have successfully synthesized bulk single crystals of S0.66(2)WS2 using a topochemical method, confirming the successful intercalation of sulfur into the interlayer space of M-WS2, which induces hole doping. The material exhibits superconductivity with a transition temperature of 6.5 K, making it the first anion-intercalated/hole-doped TMD material. This innovative approach to achieving hole doping through anion intercalation offers significant potential for application to other TMDs, enabling better control over their properties and potentially uncovering new quantum phenomena. This work marks a major step forward in the exploration and modulation of TMD-based materials. [ABSTRACT FROM AUTHOR]

A family of heteroleptic paddlewheel diruthenium complexes has been designed to obtain a chiral arrangement of the donor atoms of their equatorial ligands around the metal–metal bond axis. In order to do so, the non-symmetric ligands 2-hydroxy-6-methylpyridinate (hmp) and 2-amino-6-methylpyridinate (amp) were employed to obtain the following four axially chiral compounds: cis-[Ru2Cl(μ-DPhF)2(μ-hmp)(μ-OAc)] (Ruhmp), cis-[Ru2Cl(μ-DPhF)2(μ-amp)(μ-OAc)] (Ruamp), cis-[Ru2Cl(μ-DAniF)2(μ-hmp)(μ-OAc)] (Ru′hmp) and cis-[Ru2Cl(μ-DAniF)2(μ-amp)(μ-OAc)] (Ru′amp) (DPhF = N,N′-diphenylformamidinate, DAniF = N,N′-bis(p-methoxyphenyl)formamidinate). All the compounds were studied by single crystal X-ray diffraction, confirming that a racemic mixture containing only one of the two possible regioisomers was obtained in all cases. A general nomenclature system for naming the full configuration of intrinsically chiral paddlewheel molecules is proposed using the C/A convention. In addition, electronic spectroscopy and cyclic voltamperometry data demonstrate the electronic tunable nature of this new platform. Overall, these results provide a novel example of robust and tunable chirality, which is of potential interest to be further exploited. [ABSTRACT FROM AUTHOR]

A series of Zn(II) complexes, [Zn(MTS)2(TMEDA)] (1), [Zn(MTS)2(2,2′-bipy.)] (2), [Zn(MTS)2(1,10-phen.)] (3) and [Zn(MTS)2(4,4-bipy.)2]n (4), where MTS = methylthiosalicylate, TMEDA = tetramethyl ethylenediamine, bipy. = bipyridyl, and phen. = phenanthroline, have been synthesized and characterized by single crystal X-ray analysis and other spectroscopic techniques. The geometry of complex 3 is distorted square pyramidal around the Zn center, while complex 2 has distorted trigonal bipyramidal geometry. Complexes 1 and 4 show distorted tetrahedral geometry, of which complex 4 has a zig-zag polymeric structure. Due to differences in geometries, these Zn complexes are expected to exhibit differences in their biological activities. We have carried out studies on the DNA and protein binding, anticancer activity and cytotoxicity of these complexes. The anticancer activities were cell-line dependent; however, complex 4 was found to be the most active complex. [ABSTRACT FROM AUTHOR]

The incorporation of trinitrophenyl-modified 1,3,4-oxadiazole fragments is commonly observed in high-energy molecules with heat-resistant properties. This study explores the strategy of developing heat-resistant energetic materials by incorporating trinitrophenyl and an azo group into 1,3,4-oxadiazole, which involved the synthesis and characterization of (E)-1,2-bis(5-(2,4,6-trinitrophenyl)-1,3,4-oxadiazol-2-yl)diazene (2), N-(5-(2,4,6-trinitrophenyl)-1,3,4-oxadiazol-2-yl)nitramide (3), and the energetic salts of 3. Characterization techniques employed included 1H and 13C NMR, IR and elemental analysis. Additionally, the structures of 2 and 3 were validated using single crystal X-ray analysis. To further understand the physical and chemical characteristics of these novel energetic compounds, various calculations and measurements were performed. Compound 2 exhibits excellent thermostability (Td = 294 °C), which is comparable to that of traditional heat-resistant explosive HNS (Td = 318 °C). But 2 is insensitive towards impact (>40 J) and friction (>360 N), surpassing HNS (5 J, 240 N), suggesting that compound 2 deserves further investigation as a potential heat-resistant explosive. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have multiple optoelectronic functions because of their intriguing photophysical properties. Unfortunately, their extensive application prospects are limited by their high toxicity and instability. For these reasons, it is significant to assemble novel lead-free halides with high-performance luminescence properties. Environment-friendly In3+-based halides are gaining increasing interest because of their high stabilities and photoluminescence quantum yields (PLQYs). In this research work, we synthesized a zero-dimensional (0D) hybrid indium chloride single crystal of [1-Me-Pipz]2[InCl6]Cl·H2O (1-Me-Pipz = protonated 1-methylpiperazine) that demonstrated strong self-trapped exciton (STE)-associated broadband yellow light emission with a sufficient PLQY of 51.58%. Moreover, [1-Me-Pipz]2[InCl6]Cl·H2O exhibits extremely excellent structural and spectral stability in a variety of harsh environments. Importantly, the outstanding optoelectronic characteristics allow indium perovskite to be used for the successful fabrication of white light-emitting diodes (WLEDs) with a high color rendering index of 86.4. This work enriches the literature on indium halide perovskites and provides a novel viewpoint for the possible applications of 0D In3+ perovskite-based luminescent materials. [ABSTRACT FROM AUTHOR]

Despite that the reported CaO–Ta2O5 phase diagram indicates its incongruent melting behavior, for the first time, we found that bulk single crystals of non-centrosymmetric CaTa4O11 can be grown successfully by the floating-zone method. The as-grown crystal rods (Φ 5–6 mm) have a black and colorless transparent appearance in Ar and O2 growth atmospheres, respectively. Consequently, the O2 atmosphere was selected to optimize its bulk crystal growth. The CaTa4O11 single crystals show good crystallinity with a symmetric X-ray rocking curve for the 004 diffraction peak with an FWHM of 72′′. For this new hexagonal bulk single crystal, its anisotropic optical, dielectric, and thermal properties were characterized. The crystal has a UV cut-off edge at 272 nm and a visible transmittance of ∼75% till 800 nm. When excited by both 254 nm UV and X-ray, it shows a broad-band emission with a peak wavelength of around 427 nm. The dielectric constants ε11 and ε33 were found to be 30 and 52.3, respectively at 1 kHz. Meanwhile, the thermal conductivity along the c-axis is 5.69 W m−1 K−1, which is 1.8 times higher than that along the a-axis, which measures 3.19 W m−1 K−1 at room temperature. [ABSTRACT FROM AUTHOR]

Herein, (CH3)4NMnCl3 doped with Sb3+ single crystals were grown at room temperature. The crystal structure was confirmed by the single-crystal X-ray diffraction at 293 K. The doping of Sb3+ not only improves the excitation intensity in the blue-light region but also red emission only from Mn2+. The emission intensity (Ie) of (CH3)4NMnCl3:0.5%Sb3+ is about 1.5 times higher than that of (CH3)4NMnCl3. The internal and external quantum yield (IQY and EQY) values excited by 450 nm light for the former are 78.6% and 16.0%, which are much higher than those of the latter (56.3% and 10.7%), indicating that Sb3+ can effectively transfer energy to Mn2+. Moreover, the doping of Sb3+ is beneficial to the thermal stability. The Ie of (CH3)4NMnCl3:0.5%Sb3+ at 150 °C is about 1.2 times higher than that of (CH3)4NMnCl3 at 25 °C. Meanwhile, the white LED based on (CH3)4NMnCl3:0.5%Sb3+ also exhibits good optoelectronic performance. Hence, this work provides a new strategy to explore hybrid manganese(II) chlorides for white LEDs. [ABSTRACT FROM AUTHOR]

In this paper, four original ternary neodymium complexes, [Nd(hth)3(L)x] (where x = 1 or 2; hth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione and L = 1,10-phenanthroline (phen, 1), 5-bromo-1,10-phenanthroline (Brphen, 2), 5-chloro-1,10-phenanthroline (Clphen, 3), and triphenylphosphine oxide (tppo, 4), are reported. The complexes are synthesised by a two-step method and characterized thoroughly. The single crystal X-ray diffraction (SC-XRD) analysis is performed only for complex 4 due to the good quality of its crystals. The SC-XRD analysis indicates that complex 4 possesses an eight-coordinate structure in the solid state, having three hth and two tppo ligands. The 1H NMR analysis indicates that complexes 1–4 exhibit nine-coordinate structures in solution, having one coordinated water molecule besides hth and ancillary ligands. The Sparkle/PM7 optimized structures of the complexes are also presented, and complex 4 is compared with its crystal structure. Shape analyses reveal that complexes 1, 2, and 3 adopt biaugmented trigonal prism geometry, while complex 4 exhibits biaugmented trigonal prism J50 geometry. The photophysical investigations of the complexes were conducted in both solution and PMMA films in the near infrared (NIR) region. The results show that the hth ligand serves as an effective sensitizer and phen is the best antenna ligand. The TGA/DTA analysis indicates that the complexes are stable up to ∼200 °C, indicating their possible use in optoelectronic devices. Therefore, complex 4 is used as an emitting layer in a NIR-organic light-emitting device (OLED) with the following structure: ITO/MoO3 (2 nm)/β-NPB (30 nm)/TcTa:[complex 4] (20 nm, 10 wt%)/TPBi:[complex 4] (10 nm, 10 wt%)/TPBi (25 nm)/LiF (0.1 nm)/Al (100 nm). [ABSTRACT FROM AUTHOR]

Herein, (CH3)4NMnCl3 doped with Sb3+ single crystals were grown at room temperature. The crystal structure was confirmed by the single-crystal X-ray diffraction at 293 K. The doping of Sb3+ not only improves the excitation intensity in the blue-light region but also red emission only from Mn2+. The emission intensity (Ie) of (CH3)4NMnCl3:0.5%Sb3+ is about 1.5 times higher than that of (CH3)4NMnCl3. The internal and external quantum yield (IQY and EQY) values excited by 450 nm light for the former are 78.6% and 16.0%, which are much higher than those of the latter (56.3% and 10.7%), indicating that Sb3+ can effectively transfer energy to Mn2+. Moreover, the doping of Sb3+ is beneficial to the thermal stability. The Ie of (CH3)4NMnCl3:0.5%Sb3+ at 150 °C is about 1.2 times higher than that of (CH3)4NMnCl3 at 25 °C. Meanwhile, the white LED based on (CH3)4NMnCl3:0.5%Sb3+ also exhibits good optoelectronic performance. Hence, this work provides a new strategy to explore hybrid manganese(II) chlorides for white LEDs. [ABSTRACT FROM AUTHOR]

Despite that the reported CaO–Ta2O5 phase diagram indicates its incongruent melting behavior, for the first time, we found that bulk single crystals of non-centrosymmetric CaTa4O11 can be grown successfully by the floating-zone method. The as-grown crystal rods (Φ 5–6 mm) have a black and colorless transparent appearance in Ar and O2 growth atmospheres, respectively. Consequently, the O2 atmosphere was selected to optimize its bulk crystal growth. The CaTa4O11 single crystals show good crystallinity with a symmetric X-ray rocking curve for the 004 diffraction peak with an FWHM of 72′′. For this new hexagonal bulk single crystal, its anisotropic optical, dielectric, and thermal properties were characterized. The crystal has a UV cut-off edge at 272 nm and a visible transmittance of ∼75% till 800 nm. When excited by both 254 nm UV and X-ray, it shows a broad-band emission with a peak wavelength of around 427 nm. The dielectric constants ε11 and ε33 were found to be 30 and 52.3, respectively at 1 kHz. Meanwhile, the thermal conductivity along the c-axis is 5.69 W m−1 K−1, which is 1.8 times higher than that along the a-axis, which measures 3.19 W m−1 K−1 at room temperature. [ABSTRACT FROM AUTHOR]

Numerical simulations are frequently utilized to investigate and optimize the complex and hardly in situ examinable Physical Vapor Transport (PVT) method for SiC single crystal growth. Since various process and quality-related aspects, including growth rate and defect formation, are strongly influenced by the thermal field, accurately incorporating temperature-influencing factors is essential for developing a reliable simulation model. Particularly, the physical material properties of the furnace components are critical, yet they are often poorly characterized or even unknown. Furthermore, these properties can be different for each furnace run due to production-related variations, degradation at high process temperatures and exposure to SiC gas species. To address this issue, the present study introduces a framework for efficient investigation and calibration of the material properties of the PVT simulation by leveraging machine learning algorithms to create a surrogate model, able to substitute the computationally expensive simulation. The applied framework includes active learning, sensitivity analysis, material parameter calibration, and uncertainty analysis. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) van der Waals (vdW) materials with promising electrical, magnetic, optical, and mechanical properties have shown great potential for next-generation electronics and spintronics. Among them, vdW Fe1+xTe with varying Fe contents exhibits exotic quantum phenomena such as magnetism and superconductivity. However, they are still underexplored for Fe1+xTe with sufficiently-high Fe contents, and the electrical transport properties of Fe1+xTe crystals with higher Fe contents are still unknown. Here, we grow a vdW antiferromagnetic crystal Fe1.3Te with a Néel temperature of ∼66 K by a Sn/Te-flux method. The as-grown Fe1.3Te has the highest Fe content (x = 0.3) compared to known Fe1+xTe systems, and shows a typical structural phase transition at ∼49 K. As the temperature increases, a transition from electron-dominated to hole-dominated charge carriers is observed in exfoliated Fe1.3Te nanosheets, with a decrease in transition temperature from ∼44 to ∼38 K by reducing the thickness from 323 to 19 nm. These findings provide opportunities for the study of Fe-based vdW magnets and their potential applications. [ABSTRACT FROM AUTHOR]

A chalcone based molecular crystal, (E)-1-(2-thienyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one, has been synthesised and analyzed with SXRD, PL-studies, 1H-NMR, 13C-NMR, DSC, TGA, DTA, SEM, IR and PXRD. The compound crystallizes in an orthorhombic crystal system with the space group Pna21 and a short axis of 4.1184(2) Å. The single crystal exhibits three molecular properties, such as fluorescence (green light emission, λ = 537.21 nm), elastic bendability under mechanical force, and photoinduced bending under light (λmax = 347 nm). The photoinduced bending is a consequence of [2 + 2] dimerization between the two parallelly-oriented molecules in the single crystal. Interestingly, after the dimerization, the photoluminescence properties and elastic bendability are extinct. The transparent emissive elastic single crystal transforms into an amorphous bent brittle solid with an arc morphology. The mechanism for this rare observation is analyzed by following the variable time light exposure PXRD pattern. During the [2 + 2] dimerization, the amorphous dimer phase randomly formed along the needle releases strain at a slow pace throughout the crystal, and the needle turns into a permanently bent solid. [ABSTRACT FROM AUTHOR]

The document is a contents list from the journal CrystEngComm, focusing on the design and understanding of solid-state and crystalline materials. It includes highlights, communications, papers, and information on various research topics such as metal-organic frameworks, crystal growth, and hydrogen storage. The journal aims to connect the world with the chemical sciences and invest profits back into the chemistry community, showcasing a diverse range of scientific research in the field. [Extracted from the article]

In this paper, a promising method for growing large-sized and high-quality Mg2SiO4 single crystals was explored, and a transparent Mg2SiO4 single crystal, 30 mm in diameter and 80 mm in length, was successfully grown by the Czochralski method. The morphology of dislocation was studied by chemical etching and explained by surface energy based on the density functional theory (DFT) method. And the anisotropy of its thermodynamic and optical properties was studied. The experimental results showed a maximum Mohs hardness of 6.84 and the highest thermal conductivity of 11.73 W m−1 K−1, indicating that Mg2SiO4 has higher hardness and better thermal properties. Furthermore, the refractive index curves along the three principal axes in the range of 200–1700 nm and transmittance curves in the range of 200–2500 nm were obtained. The maximum phonon energy of the Mg2SiO4 crystal was determined. Finally, the band structure and density of states (DOS) were calculated based on the DFT method. These results provide an important reference for the application of Mg2SiO4 as a near-infrared tunable laser crystal host. [ABSTRACT FROM AUTHOR]

Herein, we describe the synthesis of a new mixed transition metal sulfide, Ba4FeCuS6, using two methods: (a) the high-temperature reaction of elements under vacuum and (b) the reaction of metal oxides and carbonates under flowing CS2 at high temperatures. Both methods successfully produced polycrystalline phases of the quaternary sulfide. Single crystals of the title phase were prepared by heating the polycrystalline sample with a Pb flux followed by slow cooling of the reaction mixture. The Ba4FeCuS6 structure adopts the monoclinic crystal system (space group: P21/n). The partitioning of the atomic charges of the sulfide can be easily done considering the Fe(III) species in the structure, i.e., [Ba(II)]4[Fe(III)][Cu(I)][S(− II)]6. The Cu atoms, Cu1 and Cu2, of the structure are distributed at two split positions. Four sulfur atoms are bonded to each Fe atom, forming a distorted tetrahedral geometry. In contrast, only three S atoms are part of the coordination polyhedron of each Cu atom to stabilize the trigonal planar geometry of the S atoms. The FeS4 and Cu1(S3)/Cu2(S3) polyhedral units are interconnected by corner sharing to create anionic pseudo-zero-dimensional units. The Ba(II) cations neutralize the negative charges on these [FeCu1–xS6](x+8)− units. Each Ba atom is surrounded by seven S atoms that form a distorted mono-capped trigonal prismatic geometry. The polycrystalline Ba4FeCuS6 is semiconducting with a direct bandgap of 1.06(2) eV. The magnetic studies of the sample show an antiferromagnetic transition below 30 K. It will be interesting to explore the photovoltaic properties of Ba4FeCuS6 in the future as it is a direct bandgap semiconductor with Eg ∼ 1 eV. [ABSTRACT FROM AUTHOR]

The covalency of f-block elements is particularly important for us to understand the bonding nature of their chemical bonds. In this work, a series of isostructural 4f and 5f complexes: [M(TrapenTMS)(OSiMe3)] (M = Ce (2Ce), Th (2Th), U (2U)); TrapenTMS = N(CH2Ph(o-NSiMe3)3) are synthesized through a salt-elimination method. These 2M complexes were characterized by single crystal X-ray diffraction, NMR, FT-IR, and UV-vis-NIR spectroscopies. The theoretical calculation based on density functional theory shows that the 4f/5f orbitals play a key role in the M–O bonding interaction and the covalency follows the trend of Ce–O < Th–O < U–O. [ABSTRACT FROM AUTHOR]

High-quality transparent cubic lutecia-stabilized zirconia (LSZ) and LSZ:Yb0.25Tm0.5Ho0.03 single crystals were fabricated by the OFZ (optical floating zone) method for the first time. For comparison, YSZ and YSZ:Yb0.25Tm0.5Ho0.03 single crystals were also fabricated. The transmittance of the LSZ single crystal (80.7%) is slightly lower than that of the YSZ single crystal (86.3%) in the visible light region, which is attributed to the LSZ single crystal with a higher density (6.604 g cm−3) in comparison with that of the YSZ single crystal (5.973 g cm−3). No absorption peaks were observed in the transmission and absorption spectra of LSZ and YSZ within 200–1100 nm, indicating that both crystals are excellent host crystals. The density of LSZ:Yb0.25Tm0.5Ho0.03 single crystals (6.596 g cm−3) is also higher than that of YSZ:Yb0.25Tm0.5Ho0.03 single crystals (6.005 g cm−3). The absorption spectra of LSZ:Yb0.25Tm0.5Ho0.03 and YSZ:Yb0.25Tm0.5Ho0.03 single crystals exhibited several absorption peaks at 363, 453, 678, and 785 nm and a strong broad absorption band within 850–1000 nm. The upconversion photoluminescence (UCPL) spectrum of the LSZ:Yb0.25Tm0.5Ho0.03 single crystal excited at 980 nm exhibited several emission peaks at 308, 373, 488, 540, 550, 655 and 794 nm; similar emission peaks were observed in the UCPL spectrum of the YSZ:Yb0.25Tm0.5Ho0.03 single crystal. The intensities of the emission peaks of the former are higher than those of the corresponding peaks of the latter, which is due to the former having a higher density and lower phonon energy in comparison with the latter. Power curves indicated that the 308 and 373 nm emissions are 4-photon upconversion processes, the 488 nm emission is a 3-photon process, and the 540 nm and 655 nm emissions are 2-photon processes. These results indicate that under the excitation at 980 nm, the LSZ:Yb0.25Tm0.5Ho0.03 single crystal has high efficiency over the YSZ:Yb0.25Tm0.5Ho0.03 single crystal in ultraviolet and visible light emissions. [ABSTRACT FROM AUTHOR]

In this paper, we report the synthesis of six novel triazole-based heteroscorpionate ligands based on heterocycle metathesis reactions and their iron(II) complexes. Single crystal structure analyses were performed, the spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover–structural relationships were compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post-synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior at room temperature. The profile of the SCO curve can be explained by the presence of only relatively weak H bonds, spreading only in one dimension. Among the interesting spin transition behaviors observed for the different complexes, such stable, complete and gradual spin crossover at room temperature makes this neutral complex a good candidate for sublimation and future investigation as an active element notably for thermoreflectance-based surface microthermometry applications. [ABSTRACT FROM AUTHOR]

Supramolecular gels are unique materials formed through the self-assembly of molecular building blocks, typically low molecular weight gelators (LMWGs), driven by non-covalent interactions. The process of crystallization within supramolecular gels has broadened the scope of the traditional gel-phase crystallization technique offering the possibility of obtaining crystals of higher quality and size. The broad structural diversity of LMWGs allows crystallization in multiple organic and aqueous solvents, favouring screening and optimization processes and the possibility to search for novel polymorphic forms. These supramolecular gels have been used for the crystallization of inorganic, small organic compounds of pharmaceutical interest, and proteins. Results have shown that these gels are not only able to produce crystals of high quality but also to influence polymorphism and physicochemical properties of the crystals, giving rise to crystals with potential new bio- and technological applications. Thus, understanding the principles of crystallization in supramolecular gels is essential for tailoring their properties and applications, ranging from drug delivery systems to composite crystals with tunable stability properties. In this review, we summarize the use of LMWG-based supramolecular gels as media to grow single crystals of a broad range of compounds. [ABSTRACT FROM AUTHOR]

In this study, we present a novel laser-based technique for in situ U–Pb, (U–Th)/He, and fission track (FT) triple dating for apatite and other U-rich accessory minerals. This approach allows for obtaining three ages with different closure temperatures on a single crystal, significantly enhancing spatial resolution and analytical productivity. Our new workflow employs an Autoscan System for FT analysis, a ResoChron system for He determination, and an LA-ICP-MS system for parent isotope and U–Pb age measurements. We describe the sample preparation, instrument parameters, and data reduction for apatite in detail. Using a sample–standard bracketing approach to determine the pairwise factor κ, we significantly improved reproducibility, particularly by replacing volume with depth in helium pit measurement. Additionally, we found that chemical etching in FT dating can reduce (U–Th)/He age by removing the surrounding He, necessitating a second polishing for samples with high track density. This in situ triple dating method has been successfully applied to five large apatite crystals, improving analytical efficiency and resolving grain-to-grain age discrepancy. [ABSTRACT FROM AUTHOR]

Topological antiferromagnetic Mn3Sn crystals exhibit notable magnetic and transport properties, comparable to ferromagnets, and undergo various intriguing magnetic phase transitions during heating or cooling. The spin structures of Mn3Sn crystals are highly influenced by growth conditions and the stoichiometric ratio of Mn and Sn, which in turn affect the phase transition temperature and the transport signatures. In this work, we employed the flux method, carefully controlling factors such as melting temperature, cooling rate, sampling temperature, vacuum, and composition, and fabricated Mn2.991Sn1.009 bulk single crystals successfully. The size of the resulting single crystal after cutting is 6 × 5 × 3 mm3. The microstructure, magnetic and transport properties of the prepared single crystals were characterized parallel to and perpendicular to the z-axis. A strong and a weak magnetic phase transition were observed at 200 K and 280 K, respectively. Our results indicate that the magnetic phase transition of Mn3Sn crystals at 200 K involves a switch in the easy-axis of magnetization from in-plane to out-of-plane, corresponding to the anomalous Hall resistance peak at 200 K. These results show a clear correlation between the spin structure and Berry curvature in Mn3Sn crystals, which significantly affect the magnitude of the anomalous Hall effect. [ABSTRACT FROM AUTHOR]

Two Mn-phosphinophosphinine complexes were synthesised from reaction of the proligand with [MnBr(CO)5] at 80 °C for 2 h; 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine manganese tricarbonyl bromide (2TMS) and 2-diphenylphosphino-3-methyl-phosphinine manganese tricarbonyl bromide (2H). 31P{1H} NMR spectroscopy revealed characteristic chemical shifts for the phosphinine and phosphine donors bound to Mn (255.4 and 23.7 ppm for 2TMS; 234.2 and 24.8 ppm for 2H), and single crystal X-ray diffraction established the structure of the chelating complex 2TMS. Rapid reaction of both complexes with water was observed with 2TMS reacting to eventually yield a single product, syn-3TMS, from the syn-1,2-addition of water across the P＝C multiple bond on the bromide face, confirmed by X-ray diffraction for both an unsolvated and solvated structure, where MeOH was found to be H-bonding to the P-OH functionality. The reaction of 2R with dry methanol gave multiple products that were not in equilibrium with each other, and the molecular structure of one isomer was definitively established by X-ray diffraction as an unusual 1,4-addition product (1,4-4TMS). However, reaction of 2R with methanol in the presence of trace water showed that hydrolysis products 3R were formed preferentially. Both phosphinine complexes acted as pre-catalysts for the Guerbet upgrading of methanol/ethanol to isobutanol at 180 °C over 90 h, giving yields of isobutanol (based on moles of ethanol) of 22% for 2TMS and 27% for 2H. This is superior to known Mn dppm complexes [dppm = bis(diphenylphosphino)methane], including the 21% yield recorded for the best derivative [MnBr(κ2-PPh2C(H)PhPPh2)(CO)3] shown to date. [ABSTRACT FROM AUTHOR]

We report a novel series of chiral monometallic dithiocarbamate complexes with pendant phenolic groups, formulated as [M{κ2S^S-S2CN(CH2PhOH)(CH(S-CH3))(NaPh)}2] (M = Ni(II) S,S-1, Cu(II) S,S-2, Zn(II) S,S-3) and [M{κ2S^S-S2CN(CH2PhOH)(CH(R-CH3))(NaPh)}2] (M = Ni(II) R,R-4, Cu(II) R,R-5, Zn(II) R,R-6). These compounds were synthesized through a process involving chiral amino precursors S-HL1, R-HL2, CS2 and the corresponding metal acetates. All the compounds have been characterized by microanalysis and standard spectroscopic methods such as 1H and 13C{1H}NMR, IR, UV-visible absorption and EPR spectroscopy. The spectral data suggest a square planar coordination geometry around the nickel(II) and copper(II) centers and a tetrahedral coordination geometry around zinc(II), which is corroborated by density functional theory calculations. The unprecedented molecular structures of imine precursors S-I, R-I and Ni(II)-dithiocarbamate complex S,S-1 were elucidated by single crystal X-ray diffraction (SCXRD), and their crystal packing patterns were studied. Evidently, the change in chirality could not induce changes in the donor–acceptor sites of S-I and R-I, and their molecules are primarily stabilized by O–H⋯N and C–H⋯π interactions, forming a 2D sheet-like structure in the ab-plane. Notably, the chiral S,S-1 complex crystallized in a monomeric achiral space group (triclinic, P1) in which two dithiocarbamate ligands are bonded to the nickel(II) ion in a S^S chelating mode forming a square planar geometry around the metal center. The photophysical properties of all the compounds have been investigated using UV-visible absorption, emission, and thermogravimetric analyses. Compounds exhibited intense blue photoluminescence with maximum emissions in the 330–336 nm region upon excitation in the UV region. A molecular docking study was performed to validate the potentials of these compounds in protein–ligand interactions against B-DNA Dodecamer (PDB Id: 1BNA) and cyclins (PDB Id: 1w98), which are indeed essential proteins of the cell cycle, and their proper functioning is necessary for the human health. [ABSTRACT FROM AUTHOR]

Scanning probe microscopy (SPM) and advanced atomic force microscopy (AFM++) have become pivotal for nanoscale elucidation of the structural, optoelectronic and photovoltaic properties of halide perovskite single crystals and polycrystalline films, both under ex situ and in situ conditions. These techniques reveal detailed information about film topography, compositional mapping, charge distribution, near-field electrical behaviors, cation–lattice interactions, ion dynamics, piezoelectric characteristics, mechanical durability, thermal conductivity, and magnetic properties of doped perovskite lattices. This article outlines the advancements in SPM techniques that deepen our understanding of the optoelectronic and photovoltaic performances of halide perovskites. [ABSTRACT FROM AUTHOR]