Bi Cl Research Articles

Eu3+ doped Cs–Bi–Cl perovskite quantum dots with diverse crystal structures for metal ion detection

The accumulation of heavy metal ions in the human body sharply affects health, drawing global attention. Consequently, there is an urgent need to develop environmentally-friendly and non-toxic metal ion fluorescent sensing probes. Herein, two fluorescent probes based on Cs–Bi–Cl perovskite quantum dots (PeQDs) with distinct structures, namely Cs3BiCl6:Eu3+ (3-1-6-E) and Cs3Bi2Cl9:Eu3+ (3-2-9-E), were successfully synthesized by using the ligand-assisted re-precipitation (LARP) method for detecting Cu2+ and Fe3+ ions in ethanol. Both PeQDs exhibit polychromatic emission, including feature emission around 505 nm and distinctive emission from Eu3+ ions in the long-wavelength region, making them suitable for ratiometric fluorescent probes. Significantly, both probes displayed excellent linear relationship with correlation coefficients of 0.998 (3-1-6-E) and 0.985 (3-2-9-E), respectively. The limit of detection (LOD) reached 6.23 μM (3-1-6-E) and 4.55 μM (3-2-9-E). Notably, the 3-2-9-E quantum dots (QDs) successfully detected Fe3+ ions in ethanol, owing to their unique photo-quenching and photo-recovery phenomena. The detection results exhibited excellent linear fitting, with a correlation coefficient of 0.996 and a low LOD of 3.6 μM. Furthermore, compared to undoped PeQDs, Eu3+ ion-doped PeQDs demonstrate strongly enhanced luminescence intensity and excellent photo-stability. This work expands the potential applications of lead-free PeQDs while simultaneously improving their luminescent properties.

Broadband near infrared emission in Cr3+: Cs2AgBiCl6 double perovskite halides

Near Infra-red phosphors with broad emission band, high thermal stability and excellent efficiency are required in various bioimaging applications. In this study, we report the design and chemical reflux synthesis of a new family of Cr3+: Cs2AgBiCl6 double perovskites. In detail this article focuses on the impact of Cr3+ doping on the crystal structure, optical and vibrational properties of Cs2AgBiCl6 double perovskites. Different concentrations of Cr3+ doped Cs2AgBiCl6 double perovskites were analyzed using UV–Visible, Raman, Photoluminescence (PL), PL excitation, time resolved PL, X-ray photoelectron spectroscopy. Morphological analyses were carried out using scanning and transmission electron microscopies. XRD spectra reveals that the cubic symmetry remains unaltered upon Cr3+ doping. Raman and Rietveld analysis show that the Bi–Cl bond decreases upon Cr3+ incorporation. Optical absorption studies reveal a decrease in bandgap from 2.76 to 2.66 eV upon Cr3+ doping. PL spectroscopy of Cr 3+:Cs2AgBiCl6 exhibits a broad near infrared (NIR) emission band at 973 nm with an FWHM of 186 nm at 355 nm excitation. This demonstrates the promising prospects for NIR light emitting diode and bioimaging applications of Cr3+:Cs2AgBiCl6 double perovskites.

Catenated (Bi)n(n=2, 3, 4) Complexes with Formally Monovalent Bismuth Centres

AbstractThe reduction of Bi(III) and Bi(II) compounds supported by the NONR‐ligand (NONR=[O(SiMe2NR)2]2−; R=Dipp=2,6‐iPr2C6H3,tBu) afforded species in which the metal was present in a range of formal oxidation‐states. Cyclic voltammetry performed on the Bi(II) radical [Bi(NONDipp)]⋅ indicated that the Bi(I) oxidation state was accessible, although the lifetime of the resultant species was short. Preparative scale reactions of Bi(NONDipp)Cl and excess LiBEt3H afforded the tetrametallic cluster Bi4(NONDipp)2, in which the bismuth atoms form a [1,2]‐edge missing tetrahedron. Reduction of the dibismuthane [Bi(NONtBu)]2with potassium in the presence of [2.2.2]‐cryptand generated a tribismuthinide salt containing the [{Bi(NONtBu)}2(μ‐Bi)]−anion and a non‐coordinating [K([2.2.2]‐crypt)]+cation. Reduction of isolated [Bi(NONDipp)]⋅ with the Mg(I) reagent [Mg(BDIDipp)]2(BDIDipp=[HC{C(Me)NDipp}2]−) formed the dibismuthene [Bi(μ‐NONDipp)Mg(BDIDipp)(THF)]2, with a crystallographically verified Bi=Bi multiple bond.

The Synthesis and Characterization of a Novel One-Dimensional Bismuth (III) Coordination Polymer as a Precursor for the Production of Bismuth (III) Oxide Nanorods

A novel Bi (III) coordination compound, [Bi(HQ)(Cl)4]n ((Q = pyridine-4-carbaldehyde thiosemicarbazone), was prepared in this research using a sonochemical technique. SEM, infrared spectroscopy (IR), XRD, and single-crystal X-ray analysis were utilized to analyze the Bi(III) coordination compound. The structure determined using single-crystal X-ray crystallography indicates that the coordination compound is a 1D polymer in solid state and that the coordination number of bismuth (III) ions is six, (BiSCl5), with one S donor from the organic ligand and five Cl donors from anions. It is equipped with a hemidirectional coordination sphere. It is interesting that the ligand has been protonated in the course of the reaction with a Cl- ion balancing the charge. This compound’s supramolecular properties are directed and regulated by weak directional intermolecular interactions. Through π–π stacking interactions, the chains interact with one another, forming a 3D framework. Thermolysis of the compound at 170 °C with oleic acid resulted in the formation of pure phase nanosized Bi (III) oxide. SEM technique was used to examine the morphology and size of the bismuth (III) oxide product produced.

Structure and properties of two new heteroleptic bismuth(III) dithiocabamates of the general composition Bi(S2CNH2)2X (X = Cl, SCN)

Abstract The title compounds were prepared by precipitation from acidic solutions of the reactants in acetone/water. Bi(S2CNH2)2Cl (1) crystallizes in the non-centrosymmetric trigonal space group P32 with a = 8.6121(3) and c = 11.1554(4) Å, Z = 3; Bi(S2NH2)2SCN (2) in P21/c (monoclinic) with a = 5.5600(2), b = 14.3679(5), c = 12.8665(4) Å, and β = 90.37(3)°. In the crystal structure of 1 Bi3+ is in a sevenfold coordination of two bidentate and one monodentate S2CHNH2 − anions with an asymmetric coordination pattern of five Bi–S and two Bi–Cl− bonds. The linkage of these polyhedra via common Cl–S edges leads to a 1D polymeric structure with undulated chains propagating in the direction [001]. These chains are linked by strong and medium strong hydrogen bonds forming the 3D crystal structure. In the crystal structure of 2 the Bi3+ cation is in an eightfold coordination. The polyhedron can be described as a significantly distorted tetragonal anti-prism, capped by an additional S atom. Two of these prisms share a common quadrilateral face to form a “prism-double” (Bi2S10N2). These building units are linked by common edges, and the resulting 1D infinite angulated chains propagate along [100]. By contrast to organo-dithiocarbamate compounds, where C–H···X bridges are dominant, the interchain connections in the crystal structures of 1 and 2 are formed exclusively via N–H···S, N–H···Cl, and N–H···N interactions, generating the 3D networks. A significant eccentricity of the Bi3+ cation in the crystal structures of both complexes is observed. Both compounds emit light in the orange range of the electromagnetic spectrum.

Synthesis, physicochemical properties, crystal molecular structure and DFT investigation of an organobismuth(III) bis(dimethyldithiocarbamate) and its organolithium precursor

Two new organobismuth(III) dimethyldithiocarbamates, i.e. [2-(Me2NCH2)C6H4]Bi(Cl)(S2CNMe2) (4) and [2-(Me2NCH2)C6H4]Bi(S2CNMe2)2 (5), were obtained and their potential use as single source precursors for obtaining Bi2S3 was investigated. Compound 5 shows clean decomposition to Bi2S3 in the 220–320 °C temperature range, while in the case of 4 decomposition is plagued by a potential redistribution process. DFT, NBO and Hirshfeld surface analyses were carried out for the starting material [2-(Me2NCH2)C6H4]Li (1) and the new compound 5 in order to understand the nature of intra- and intermolecular bonding interactions and the results were compared with those observed experimentally by single crystal X-ray diffraction.

Green synthesis and microcalorimetric study of a novel N-alkylation Schiff base and its bismuth(III) complex

A new N-alkylation Schiff base [N2,N6-bis(2-hydroxy-3-methoxybenzyl)pyridine-2,6-dicarboxamide] was synthesized from o-vanillin and pyridine-2,6-dicarboxamide by a solid-phase microwave green synthesis without catalyst and solvent. A new bismuth(III) complex was prepared by reaction of the ligand with BiCl3. The ligand and its bismuth(III) complex were characterized by elemental analysis, spectral techniques (1HNMR, MS, FT-IR and UV), chemical analysis, thermogravimetric analysis and molar conductance. The compositions of the ligand and its bismuth(III) complex were (C23H23N3O6) and Bi(C23H21N3O6)Cl. Moreover, the antibacterial activity of the ligand and its bismuth(III) complex against S. pombe was evaluated by bio-microcalorimetry at 32 °C. The quantitative relationship between some thermokinetic parameters (k, tG and I) with the concentration (c) of the ligand and its bismuth(III) complex was investigated. The half inhibition concentrations (IC50) of the ligand and its bismuth(III) complex were obtained as 4.63 × 10–3 mol dm−3 and 2.10 × 10–3 mol dm−3, respectively. The results showed that the antibacterial activity of bismuth(III) complex was stronger than that of the ligand. Further, the action target of bismuth(III) complex on bovine serum albumin (BSA) was studied by the molecular docking simulation method, and we found that bismuth(III) complex bounded at in the hydrophobic cavity of the substructure domain IIB of BSA.

High-throughput screening to modulate electronic and optical properties of alloyed Cs2AgBiCl6 for enhanced solar cell efficiency

The lead-free double perovskite material (viz. Cs2AgBiCl6) has emerged as an efficient and environmentally friendly alternative to lead halide perovskites. To make Cs2AgBiCl6 optically active in the visible region of solar spectrum, band gap engineering approach has been undertaken. Using Cs2AgBiCl6 as a host, band gap and optical properties of Cs2AgBiCl6 have been modulated by alloying with M(I), M(II), and M(III) cations at Ag-/Bi-sites. Here, we have employed density functional theory (DFT) with suitable exchange-correlation functionals in light of spin–orbit coupling (SOC) to determine the stability, band gap and optical properties of different compositions, that are obtained on Ag–Cl and Bi–Cl sublattices mixing. On analyzing 64 combinations within Cs2AgBiCl6, we have identified 19 promising configurations having band gap sensitive to solar cell applications. The most suitable configurations with Ge(II) and Sn(II) substitutions have spectroscopic limited maximum efficiency (SLME) of 32.08% and 30.91%, respectively, which are apt for solar cell absorber.

Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry.

We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)‐stabilized bismuth complexes, which feature low‐coordinate cationic bismuth centers with C=Bi multiple‐bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2 (9) and [(CDC)BiBr(THF)3][NTf2]2 (12), and trication [(CDC)2Bi][NTf2]3 (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2 (7) and (CDC)BiBr3 (10). Notably, the dications and trication exhibit C⇉ Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non‐reductive route to C−Bi π‐bonding character. The CDC‐[Bi] complexes (7–13) were compared with related NHC‐[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low‐coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.

Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

AbstractWe report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)‐stabilized bismuth complexes, which feature low‐coordinate cationic bismuth centers with C=Bi multiple‐bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2 (9) and [(CDC)BiBr(THF)3][NTf2]2 (12), and trication [(CDC)2Bi][NTf2]3 (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2 (7) and (CDC)BiBr3 (10). Notably, the dications and trication exhibit C Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non‐reductive route to C−Bi π‐bonding character. The CDC‐[Bi] complexes (7–13) were compared with related NHC‐[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low‐coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.

Determination of molecular properties for moscovium halides (McF and McCl)

Advanced relativistic quantum chemistry calculations were used for the first time to provide accurate determinations of fundamental molecular properties for two moscovium halides (McX, X = F and Cl). The recommended values presented here were obtained with the X2C-MMF-CCSD-T/RPF-4Z level of theory. Thus, we determined an equilibrium bond length (re) of 2.287 A, an equilibrium dipole moment (μe) of 6.59 D and a harmonic vibrational frequency (ωe) of 405 cm−1 for McF. On the other hand, the results for McCl show re, μe and ωe values equal to 2.728 A, 7.46 D and 244 cm−1, respectively. The same Mc+–X− polarity is predicted in molecules of both halides. The equilibrium dissociation energies attained in X2C-MMF-(FS)CCSD/RPF-4Z calculations are 4.04 and 3.45 eV for McF and McCl, respectively. Therefore, the Mc–F and Mc–Cl bonds are predicted to be slightly stronger than Bi–F and Bi–Cl ones, respectively. Finally, the huge values obtained for dipole moments in the molecules studied strongly suggest that moscovium halides are predominantly ionic compounds.

Synthesis of a Valen Schiff-base bismuth(III) complex and its thermokinetic studies on the growth metabolism of S. pombe

A Valen Schiff-base ligand [1,5-bis(2-hydroxy-3-methoxybenzylidene)thiocarbonohydrazide] and its bismuth(III) complex were synthesized. The compositions and structures of two compounds were characterized by elemental analysis, spectrometry (1HNMR, MS, FT-IR, and UV-visible), chemical analysis, molar conductivity, and TG–DTA analysis. The results showed that the molecular formula of Schiff base and its bismuth(III) complex was C17H18O4N4S (abbreviated as H2L, L = C17H16O4N4S) and [Bi(C17H16O4N4S)Cl·H2O] (abbreviated as [Bi(L)Cl·H2O]), respectively. Furthermore, the thermokinetic properties of the action of Schiff base and its bismuth(III) complex on the growth metabolism of S. pombe were studied by bio-microcalorimetry at 305.15 K. The growth rate constant (k), maximum heat power, generation time, inhibition ratio (I) and half inhibition concentration (IC50), and their quantitative relationship with the concentration were calculated, respectively. Experimental results indicated that both Schiff base and its bismuth(III) complex could inhibit the growth of S. pombe, but the inhibitory effect of Schiff base was stronger than that of the complex. The half inhibition concentrations of Schiff base and its bismuth(III) complex were found to be 4.17 × 10−3 mol L−1 and 6.13 × 10−3 mol L−1, respectively.

From 0D Cs3Bi2I9 to 2D Cs3Bi2I6Cl3: Dimensional Expansion Induces a Direct Band Gap but Enhances Electron–Phonon Coupling

Alternative all-inorganic halide perovskites are sought to replace the hybrid lead halide perovskites because of their increased stability. Here, the (111)-oriented defect perovskite family A3M2X9 based on trivalent M3+ is expanded through the use of mixed halides, resulting in Cs3Bi2I6Cl3. This compound shares the (111)-oriented 2D bilayer structure of α-Cs3Sb2I9 (space group P3m1), with Cl occupying the bridging positions of the bilayers and I in the terminal sites, in contrast to the parent compound Cs3Bi2I9, which consists of 0D molecular [Bi2I9]3– dimers. The increased dimensionality induces a direct band gap as calculated by density functional theory but has an absorption edge of 2.07 eV, nearly identical to the indirect band gap compound Cs3Bi2I9. Intriguingly, there is a remarkable lack of Cl orbital contribution to the band edge states of Cs3Bi2I6Cl3, despite Bi–Cl bonds binding all octahedra together. This highlights the importance of interlayer interactions in the defect perovskite family, whi...

Intramolecular Metal⋅⋅⋅π-Arene Interactions in Neutral and Cationic Main Group Compounds.

The role of intramolecular metal⋅⋅⋅π-arene interactions has been investigated in the solid-state structures of a series of main group compounds supported by the bulky amide ligands, [N(tBu Ar≠ )(SiR3 )]- (tBu Ar≠ =2,6-(CHPh2 )2 -4-tBuC6 H2 , R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the SiPh3 substituent is able to be involved in stabilizing the electrophilic metal. These group 1 metal compounds served as ligand transfer reagents to access a series of bismuth(III) halides. Chloride extraction from Bi(N{tBu Ar≠ }{SiPh3 })Cl2 using AlCl3 afforded the 1:1 salt [Bi(N{tBu Ar≠ }{SiPh3 })Cl][AlCl4 ]. This was accompanied by a significant rearrangement of the stabilizing π-arene contacts in the solid-state. Attempted preparation of the corresponding tetraphenylborate salt resulted in phenyl-transfer and generation of the neutral Bi(N{tBu Ar≠ }{SiPh3 })(Ph)Cl.

Multimetallic systems composed of CpFe(CO)2-, Cp2Re- and (RCO2)2Bi- moieties

The reaction of [Fp]2 (Fp = (η5-C5H5)(CO)2Fe) with bismuth formate was shown to proceed via Fe-Bi bond formation yielding [Fp–Bi(O2CH)2]n, 1, that could be crystallized in form of two polymorphs. These differ in the way the [Fp−Bi(O2CH)2] units are connected via bridging formate ligands to yield the respective coordination polymers. The acetate derivative [Fp–Bi(O2CCH3)2] was used as a precursor compound targeting at the construction of an additional transition metal-bismuth bond: the reaction of [Fp–Bi(O2CCH3)2] with [Cp2ReH] likely yields in the envisaged complex [Fp−Bi(O2CCH3)ReCp2] first but then undergoes further transformation due to the presence of chloride and acetic acid in solution, which lead to the formation of [Fp−Bi(Cl)ReCp2], 3, and [Cp2Re–Bi(O2CCH3)2], 4, respectively. The identity of the heterotrimetallic compound 3 was established by a single-crystal X-ray diffraction analysis, while an independent synthetic route (reaction of [Cp2ReH] with [Bi(O2CCH3)3]) was developed for 4 in order to unambiguously identify 4 also as the product of the reaction between [Fp–Bi(O2CCH3)2] and [Cp2ReH].

Raman study of order-disorder phase transition in [(C3H7)4N]3Bi3Cl12 compound

The [(C3H7)4N]3Bi3Cl12 compound that crystallizes at room temperature in a centrosymmetric triclinic system (P1¯ space group) is studied on heating up to its melting temperature. Differential scanning calorimetry investigations disclosed an irreversible phase transition at T = 414 K. Raman scattering studies (140–3500 cm−1) were investigated in the temperature range 398–438 K. A detailed analysis of the frequency, half-width and reduced intensity of the bands associated to υ(Bi–Cl) (at 254 cm−1), υ(Bi–Cl) (at 287 cm−1) and υs(N–C–C)+δs(C–N–C) (at 1034 cm−1) is quantitatively described in term of an order-disorder phase transitions. The temperature dependence of the correlation lengths of these three bands is consistent with a disordered state at high temperature. This behavior is presumably governed by the reorientational motion of the alkylammonium chains of the cations between two sites coupled with changes of interactions with the anionic groups.

Geology, petrology and geochronology of the Lago Grande layered complex: Evidence for a PGE-mineralized magmatic suite in the Carajás Mineral Province, Brazil

The Lago Grande and Luanga mafic-ultramafic complexes are part of a cluster of PGE-mineralized layered intrusions located in the Carajás Mineral Province (CMP) in the Amazonian Craton. The Lago Grande Complex is a NE-trending medium-size (12-km-long and average 1.7-km-wide) layered intrusion consisting mainly of mafic cumulate rocks (Mafic Zone) and minor ultramafic cumulates (Ultramafic Zone). Geological sections indicate that igneous layers are overturned, such that the Ultramafic Zone overly the Mafic Zone. The Ultramafic Zone, about 4 km long and 500 m wide, comprises an up to 250 m-thick sequence of interlayered harzburgite and orthopyroxenite at the base and orthopyroxenite at the top. The Mafic Zone consists of a monotonous sequence of gabbroic rocks with an estimated thickness of up to 1000 m in the central part. Primary igneous minerals of the Lago Grande Complex are partially replaced by metamorphic assemblages that indicate temperatures up to the amphibolite facies of metamorphism. This metamorphic alteration is heterogeneous and characterized by an extensive hydration that largely preserves primary textures and bulk chemical composition.The composition of the parental magma of the Lago Grande Complex has been inferred from the crystallization sequences of the intrusion and lithogeochemistry of cumulate rocks. The compositional range of cumulus Ol (Fo82.5–85.7) is consistent with a moderately primitive composition for the parental magma. Cumulus minerals in the layered rocks indicate that the sequence of crystallization in the Lago Grande Complex consists of Ol + Chr, Opx + Chr, Opx, Opx + Pl and Opx + Pl + Cpx. The early crystallization of Opx relative to Cpx suggests that the primary magma was silica saturated. Mantle-normalized alteration-resistant trace element profiles of gabbroic rocks are fractionated, as indicated by relative enrichment in LREE and Th, with pronounced negative Nb and Ta anomalies. Nd isotopic data obtained for both mafic and ultramafic lithotypes render Nd model ages between 2.94 and 3.56 Ga, with variably negative εNd (T = 2.72 Ga) values (−0.32 to −4.25). The crystallization sequence of the intrusion and the composition of cumulus minerals, together with lithogeochemical and Nd isotopic results, are consistent with an original mantle melt contaminated with older continental crust. The contamination of mafic magma with sialic crust is also consistent with intra-plate rifting models proposed in several studies of the CMP. Lithogeochemical and isotopic data from the Lago Grande Complex may also be interpreted as the result of melting an old lithospheric mantle, and alternative models should not be disregarded.PGE mineralizations occur in chromitites and associated with base metal sulfides in the Lago Grande Complex. Chromitite has the highest PGE content (up to 10 ppm) and is characterized by high Pt/Pd ratio (4.3). Mantle-normalized profile of chromitite is highly enriched in PPGE and similar to those from Middle Group (MG) and Upper Group (UG) chromitites from the Bushveld Complex. Platinum group minerals (PGM) occur mainly at the edge of chromite crystals in the Lago Grande chromitite, consisting of arsenides and sulfo-arsenides. Sulfide-bearing harzburgite samples of the Lago Grande complex have PGE content of up to 1 ppm and low Pt/Pd (0.2–0.3) ratios.The 2722 ± 53 Ma U–Pb zircon age determined in this study for the Lago Grande Complex overlaps with the crystallization age of the Luanga Complex. Previous interpretation that the Lago Grande and Luanga layered intrusions are part of a magmatic suite (i.e., Serra Leste Magmatic Suite) is now reinforced by similar fractionation sequences, comparable petrological evolution and overlapped U–Pb zircon ages. The occurrence of the same styles of PGE mineralization in the Lago Grande and Luanga complexes, together with remarkably similar chondrite-normalized PGE profiles and PGE minerals for chromitites of both complexes, support the concept that they belong to the same PGE-fertile magmatic suite.U–Pb isotope analyses of zircon crystals obtained on bright luminescent rims with typical recrystallization features reveal a cluster of concordant to slightly discordant dates pointing at 2553 ± 61 Ma. These are likely to correspond to a significant disturbance of the U–Pb system of the Lago Grande Complex during the ca. 2.55 Ga regional scale hydrothermal event associated with the origin of IOCG type deposits. Common Bi–Cl minerals associated with highly transformed PGE-mineralized zones also suggest hydrothermal alteration by the regional IOCG type system. This type of alteration identified in the Lago Grande mafic-ultramafic layered intrusions may provide the explanation for common Ni–Co anomalies identified in several Cu–Au deposits, as well as hydrothermal Au–Pd mineralizations in Carajás.

Isolation and Characterization of a Bismuth(II) Radical

AbstractMore than 80 years after Paneth’s report of dimethyl bismuth, the first monomeric BiII radical that is stable in the solid state has been isolated and characterized. Reduction of the diamidobismuth(III) chloride Bi(NONAr)Cl (NONAr=[O(SiMe2NAr)2]2−; Ar=2,6‐iPr2C6H3) with magnesium affords the BiII radical .Bi(NONAr). X‐ray crystallographic measurements are consistent with a two‐coordinate bismuth in the +2 oxidation state with no short intermolecular contacts, and solid‐state SQUID magnetic measurements indicate a paramagnetic compound with a single unpaired electron. EPR and density functional calculations show a metal‐centered radical with >90 % spin density in a p‐type orbital on bismuth.

PBiP Pincer Complexes of Platinum, Palladium, and Iridium Featuring Metal–Metal Bonds Synthesized by Oxidative Addition of Bismuth–Halide Bonds

The compound BiCl(o-PPh2-C6H4)2, PBiP-Cl, which in previous work had been shown to form complexes with pronounced M→Bi character, when metal(I) ions of group 11 or PtII and PdII ions were coordinated, behave differently in contact with late metal atoms in low oxidation states, known to easily undergo oxidative additions: Treatment of PBiP-Cl with M(PPh3)4, with M = Pt, Pd, led to the formal insertion of M into the Bi–Cl bond to yield complexes [MCl(PBiP)]. Analogues PBiP-X with X = Br, I that could be accessed behaved similarly, producing [MX(PBiP)]. Both types of complexation reactions—coordination of PBiP-Cl as an ambiphilic ligand and oxidative addition—were observed to occur when [Ir(acac)(cod)] was chosen as the precursor compound. NMR investigations clearly indicated the presence of [IrI(acac)(PBiP-Cl)] and [IrIII(acac)Cl(PBiP)] beside each other in solution, from which, however, only [IrIII(acac)Cl(PBiP)] could be crystallized. DFT results showed that both products differ only slightly in energy. R...

A new linear bismuth coordination polymer based on 1,10-phenanthroline-2,9-dicarboxylic acid: ionothermal synthesis, crystal structure and fluorescence properties.

A new linear bismuth(III) coordination polymer, catena-poly[[chloridobismuth(III)]-μ3-1,10-phenanthroline-2,9-dicarboxylato-κ(6)O(2):O(2),N(1),N(10),O(9):O(9)], [Bi(C14H6N2O4)Cl]n, has been obtained by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR spectroscopy, thermal stability studies and single-crystal X-ray diffraction. The structure is constructed by Bi(C14H6N2O4)Cl fragments in which each Bi(III) centre is seven-coordinated by one Cl atom, four O atoms and two N atoms. The coordination geometry of the Bi(III) cation is distorted pentagonal-bipyramidal (BiO4N2Cl), with one bridging carboxylate O atom and one Cl atom located in the axial positions. The Bi(C14H6N2O4)Cl fragments are further extended into a one-dimensional linear polymeric structure via subsequent but different centres of symmetry (bridging carboxylate O atoms). Neighbouring linear chains are assembled via weak C-H···O and C-H···Cl hydrogen bonds, forming a three-dimensional supramolecular architecture. Intermolecular π-π stacking interactions are observed, with centroid-to-centroid distances of 3.678 (4) Å, which further stabilize the structure. In addition, the solid-state fluorescence properties of the title coordination polymer were investigated.