Bismuth Coordination Research Articles

Ultra‐Broadband Emission in Bi/Ge Co‐Doped Silica Glass and Fiber via Bismuth Coordination Engineering

AbstractBismuth (Bi) and Germanium (Ge) co‐doped silica glass and fiber, as advanced gain media with broadband near‐infrared (NIR) emission and amplification, have promise for extending communication bandwidth. However, efficiently modulating the NIR emissions of bismuth to cover the C+L communication bands remain a significant challenge. In the study, a high‐temperature and high‐pressure reduction treatment on Bi/Ge co‐doped silica glass is employed to tailor the coordination environment around bismuth active center. This method facilitated the creation of new bismuth NIR luminescence centers, resulting in the luminescence spectrum with a peak position at 1550 nm and a FWHM exceeding 350 nm. The changes in the bismuth coordination environment are elucidated using HRTEM, photoluminescence decay, temperature‐dependent emission, EXAFS and CW‐EPR. Furthermore, the feasibility of this method in Bi/Ge co‐doped silica fiber is validated, and obtained >5 dB amplification in the range of 1400–1700 nm. This coordination engineering method holds significant potential for widespread application in Bi/Ge co‐doped silica glass and optical fiber is believed. It presents a promising prospect for expanding communication bandwidth by effectively modulating the NIR emissions of bismuth to cover the S to U communication band.

Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties.

Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin-orbit coupling and potential optoelectronics applications. Herein, four bismuth halide-based coordination complexes [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), and [Bi2I6(phen-Me)2] (4) were synthesized, characterized, and subjected to detailed photophysical studies. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and NMR studies. Spectroscopic analyses of 1-4 in solutions of different polarities were performed to understand the role of the organic and inorganic components in determining the ground- and excited-state properties of the complexes. The photophysical properties of the complexes were characterized by ground-state absorption, steady-state photoluminescence, microsecond time-resolved photoluminescence, and absorption spectroscopy. Periodic density functional theory (DFT) calculations were performed on the solid-state structures to understand the role of the organic and inorganic parts of the complexes. The studies showed that changing the ancillary ligand from chlorine (Cl) and bromine (Br) to iodine (I) bathochromically shifts the absorption band along with enhancing the absorption coefficient. Also, changing the halides (Cl, Br to I) affects the photoluminescent quantum yields of the ligand-centered (LC) emissive state without markedly affecting the lifetimes. The combined results confirmed that ground-state properties are strongly influenced by the inorganic part, and the lower-energy excited state is LC. This study paves the way to design novel bismuth coordination complexes for optoelectronic applications by rigorously choosing the ligands and bismuth salt.

Dynamic Fluorescence Sensing of Bromide Ions by Photochromic Bi(III)-Coordination Polymers Based on a Ligand Integrated by Naphthalene Diimides and Pyridinium in Solution and Films.

Bismuth(III)-based complexes have garnered increasing attention in fluorescence sensing due to their environmentally friendly and sustainable characteristics. A Bismuth(III) coordination polymer (CP),1-Cl based on a naphthalene diimides(NDI)-pyridinium is synthesized by an in situ reaction method. Notable for its sensitivity to visible light, 1-Cl shows excellent photochromic properties, and the integration of NDI and pyridinium in one ligand makes photogenerated radicals more stable. Structural analysis and theoretical calculations are employed to investigate the potential pathway of photoinduced electron transfer (ET) during the photochromic process. Notably, in aqueous solutions, 1-Cl displays an extraordinary fluorescence enhancement response to bromide ion (Br-), resulting in a distinct transition from yellow to orange in color. The potential mechanism of fluorescence sensing has been revealed through single-crystal X-ray diffraction analysis. This insight highlights a continuous substitution process where the Cl- ions are successively replaced by Br- ions. Consequently, a single-crystal-to-single-crystal transformation (SCSC) occurs, yielding the intermediate species, 1-Cl-Br, which ultimately transforms into the final product, 1-Br. Finally, the photochromic film is successfully prepared and applied to practical applications such as ink-free printing, information anti-counterfeiting, and the visual detection of Br- ions. This work combines photochromism with fluorescence sensing, broadening the research field and practical application of photochromic materials.

Two new bismuth salts with succinic acid: synthesis, structural, spectroscopic and thermal characterization.

Two novel bismuth succinate hydrates, namely, poly[[diaqua(μ3-butane-1,4-dicarboxylato)hemi(μ-butane-1,4-dicarboxylato)bismuth] monohydrate], {[Bi(C4H4O4)1.5(H2O)2]·H2O}n (1), and poly[[μ-aqua-aqua(μ3-butane-1,4-dicarboxylato)(μ-butane-1,4-dicarboxylato)-μ-oxido-dibismuth] monohydrate], {[Bi2(C4H4O4)2O(H2O)2]·H2O}n (2), have been synthesized. Their crystal structures were determined by single-crystal X-ray diffraction and the compounds were characterized by IR and Raman spectroscopy, powder X-ray diffraction and thermal analysis. The crystal structure analysis revealed that the compounds are coordination polymers, with 1 having a two-dimensional layered structure and 2 displaying a three-dimensional (3D) framework. Fully deprotonated succinate anions (C4H4O42-) in two different conformations (trans and gauche) are included in their composition. The Bi3+ cations are surrounded by O atoms from the carboxylate groups of succinate anions and aqua ligands. BiO9 coordination polyhedra in 1 are connected in pairs by edges. These pairs are bound together by bridging succinate ligands to form layers. Bismuth coordination polyhedra of two different types (BiO9 and BiO7) in 2 are connected by edges to form infinite ribbons. Ribbons of polyhedra with bridging succinate ligands form a 3D polymeric structure.

Bismuth Coordination Polymers with Fluorinated Linkers: Aqueous Stability, Bivolatility, and Adsorptive Behavior.

Bismuth metal-organic frameworks and coordination polymers (CP) are challenging to synthesize, given the poor solubility of bismuth precursors and asymmetric and labile ligation of Bi3+ due to its intrinsic lone pair. Here, we synthesize and structurally characterize three Bi3+-CPs, exploiting a tetrafluoroterephtalate (F4BDC) linker to determine the effect of high acidity on these synthesis and coordination challenges. Single-crystal X-ray diffraction characterization showed that pi-pi stacking of linkers directs framework arrangement and generally deters open porosity in the three structures, respectively featuring Bi chains (Bi chain -F 4 BDC), Bi dimers (Bi 2 -F 4 BDC) linked into chains, and Bi tetramers (Bi 4 -F 4 BDC). Powder X-ray diffraction and microscopic imaging show the high purity and stability of these compounds in water. Naphthalenedisulfonate (NDS) was used as a mineralizer in the synthesis of (Bi chain -F 4 BDC) and (Bi 4 -F 4 BDC), and studies of its role in assembly pathways yielded two additional structures featuring mixed NDS and F4BDC, respectively, linking monomer and octamer Bi nodes, and confirmed that F4BDC is the preferred (less labile) linker. Methylene blue (MB) adsorption studies show differing efficacies of the three Bi-F4BDC phases, attributed to surface characteristics of the preferential growth facets, while generally most effective adsorption is attributed to the hydrophobicity of fluorinated ligands. Finally, thermogravimetric analysis of all three Bi-F4BDC phases indicates simultaneous ligand degradation and in situ formation of volatile Bi compounds, which could be exploited in the chemical vapor deposition of Bi-containing thin films.

Synthesis, crystal structure, and topology of a polycatenated bismuth coordination polymer

Abstract Solvothermal reaction of Bi(NO3)3·5H2O with the flexible ligand 1,3,5-tris[4-(carboxyphenyl)oxamethyl]-2,4,6-trimethylbenzene (H3TBTC) in methanol at 120 °C for 1 h led to the formation of a novel coordination polymer (CP) with the composition of Bi(TBTC). The structure of the microcrystalline material was determined through three-dimensional electron diffraction (3DED) measurements and phase purity was confirmed by a Pawley refinement, elemental analysis, and thermal analysis. The compound crystallizes in the triclinic space group P 1 ‾ $P\overline{1}$ with one Bi3+ cation and one TBTC3− trianion in the asymmetric unit. Edge-sharing of BiO7 polyhedra leads to the formation of dinuclear Bi2O12 units, which through coordination to six TBTC3− ions form a layered two-periodic structure. Upon heating the material in air, the unit cell volume contracts by 9%, which is attributed to a shift in the inter-layer arrangement and to the flexibility of the building units of the structure. The compound starts to decompose at ∼300 °C. Topological analysis revealed layers consisting of 3-c and 6-c nodes, consistent with the two-periodic kgd net – the dual of the Kagome net (kgm). However, due to the non-planar nature of the Bi(TBTC) layers, adjacent layers are interlaced by polycatenation.

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.

Dinuclear complexes, a one dimensional chain and a two dimensional layer of bismuth(iii) chalcogenones for C–S cross coupling reactions

The bismuth coordination polymers derived from organochalcogenone ligands and their catalytic applications in the synthesis of annulated heterocyclic aryl thioethers have been investigated.

Harnessing Bismuth Coordination Chemistry to Achieve Bright, Long-Lived Organic Phosphorescence.

A new bismuth(III)-organic compound, Hphen[Bi2(HPDC)2(PDC)2(NO3)]·4H2O (Bi-1; PDC = 2,6-pyridinedicarboxylate and phen = 1,10-phenanthroline), was synthesized, and the structure was determined by single-crystal X-ray diffraction. The compound was found to display bright-blue-green phosphorescence in the solid state under UV irradiation, with a luminescent lifetime of 1.776 ms at room temperature. The room temperature and low-temperature (77 K) emission spectra exhibited the vibronic structure characteristic of Hphen phosphorescence. Time-dependent density functional theory studies showed that the excitation pathway arises from an energy transfer from the dimeric structural unit to Hphen, with participation from a nine-coordinate Bi center. The triplet state of Hphen is believed to be stabilized via supramolecular interactions, which, when coupled with the heavy-atom effect induced by Bi, leads to the observed long-lived luminescence. The compound displayed a solid-state quantum yield of over 27%. To the best of our knowledge, this is the first such compound to exhibit phenanthrolinium phosphorescence with such long-lived, room temperature lifetimes in the solid state. To further elucidate the energy-transfer mechanism, Ln3+ (Ln = Eu, Tb, Sm) ions were successfully doped into the parent compound, and the resulting materials exhibited dual emission from Hphen and Ln, promoting tunability of the emission color.

A new bismuth coordination polymer with proton conductivity and orange-red photoluminescence

A new highly water stable bismuth-containing coordination polymer is reported along with its structural characterizations as determined by single crystal and powder X-ray diffraction, elemental, and thermal analysis, featuring an orange-red photoluminescence, and proton conductivity. The compound, (Imi)2[Bi2(pzdc)4]·2H2O (1, pzdc2- = pyrazine-2,3-dicarboxylate; Imi = imidazolium cation), crystallizes in the monoclinic space group, P21/c (a = 14.3725(7) Å, b = 22.4499(10) Å, c = 11.5204(6) Å, and β = 91.1183(16)°), which contains 2D layers of Bi that are connected into a 3D supramolecular structure via extended hydrogen bond network. The interlayered voids are occupied by lattice water and imidazolium ions. Compound 1 is synthesized using an optimized, facile slow evaporation method leading to a water stable compound with a well-defined 1D hydrogen-bonded water feature along the crystallographic a-direction that lead to a proton conductivity of 8.41 × 10−6 S·cm−1 at 85 °C and 95% RH.

Exploring the influence of atomic level structure, porosity, and stability of bismuth(iii) coordination polymers on electrocatalytic CO2reduction

The study maps out the dependence of porosity, bismuth-to-carbon ratio and chemical stability of bismuth-based MOFs on electrocatalytic CO2reduction.

Synthesis of biological based hennotannic acid-based salts over porous bismuth coordination polymer with phosphorous acid tags.

In this paper, a novel porous polymer capable of coordinating to bismuth (PCPs-Bi) was synthesized. The Bi-PCPs was then reacted with phosphorous acid to produce a novel polymer PCPs(Bi)N(CH2PO3H2)2 which is shown to act as an efficient and recyclable catalyst. The mentioned catalyst was applied for the efficient synthesis of new mono and bis naphthoquinone-based salts of piperidine and/or piperazine via the reaction of hennotannic acid with various aldehydes, piperidine and/or piperazine, respectively. The structure of the resulting mono and bis substituted piperazine or piperidine-based naphthoquinone salts was thoroughly characterized spectroscopically. The electrochemical behavior of the products was also investigated. The presented protocol has the advantages of excellent yields (82–95%), short reaction times (4–30 min) and simple work-up.

Coordination polymers incorporating Bi(III) and 2,4,6-pyridine tricarboxylic acid and its derivatives: Synthesis, structure and topology

Bi(III) as its oxide combined with 2,4,6-pyridine tricarboxylic acid, H2pdc-COOH, and various pyridine-derived additives in dimethylformamide (dmf) under solvothermal conditions produced three novel bismuth coordination polymers, {[Bi(μ-pdc-COO)2][NH2Me2]3}n, 1, {[Bi(μ-pdc-COO)2][C5H7N2]3·C5H6N2}n, 2, and {[Bi2(μ-pdc-COO)2(μ-pdc-COOH)(pdc-COOH)][NH2Me2]4·2dmf·NHMe2}n, 3. The anionic coordination network topologies are two-dimensional, chains-of-loops and ladders, respectively, but the local 8-coordinate environments about the bismuth(III) centres are in each case between that of a square antiprism and that of a hexagonal bipyramid. When the 4-carboxy substituent in H2pdc-COOH is replaced by another potentially coordinating substituent to give 4-R-2,6-pyridine dicarboxylic acid, H2pdc-R (R = OH, NH2, Cl), the salts obtained contain discrete centrosymmetric dinuclear 8-coordinate bismuth anions with either double O-bridges between the metal centres, [Bi2(μ-pdc-R)2(pdc-R)2(dmf)2][NH2Me2]2 (R = OH, NH2), 4 and 5, or double carboxylate bridges with one long Bi–O bond, [Bi2(μ-pdc-NMe2)2(pdc-NMe2)2(dmf)2][NH2Me2]2, 6 (R = Cl, but replaced by dimethylamine during the reaction). The structures and supramolecular networks of 1–6 are described and compared as an exploration of alternatives to the conventional carboxylate-based organic linking units.

Crystal structure and luminescence properties of a new dinuclear bismuth(III) coordination polymer containing three types of ligands

Abstract A new dinuclear bismuth(III) coordination polymer {[Bi(H2O)]2(C7H3NO4)2(C12H8N2)2(N3)2·2H2O} n (1) containing three types of ligands has been synthesized using a solvothermal method and characterized by infrared (IR) spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray single-crystal structural analysis. The compound can be viewed as a three-dimensional supramolecular network that is constructed by Bi3+ cations, N3 − anions, pyridine-2,5-dicarboxylate (2,5-pdc2−), and 1,10-phenanthroline (phen) ligands. Moreover, the luminescence properties, quantum yield, luminescence decay, and thermal stabilities of 1 were also investigated.

Luminescence tuning and single-phase white light emitters based on rare earth ions doped into a bismuth coordination network

Luminescence-tuneable multicolour of coordination network materials by changing the doping concentration of the RE3+double-doped [Bi(HPyr)] anhydrous matrix.

A two-dimensional bismuth coordination polymer with tartaric acid: Synthesis, characterization and thermal decomposition to Bi2O3 nanoparticles

A two-dimensional bismuth coordination polymer with tartaric acid: Synthesis, characterization and thermal decomposition to Bi2O3 nanoparticles

Bismuth coordination polymers: from centuries-old medicines to unprecedented topological complexity

Bismuth coordination polymers : from centuries-old medicines to unprecedented topological complexity

Crystal Structure of AgBi2I7 Thin Films.

Synthesis of cubic-phase AgBi2I7 iodobismuthate thin films and fabrication of air-stable Pb-free solar cells using the AgBi2I7 absorber have recently been reported. On the basis of X-ray diffraction (XRD) analysis and nominal composition, it was suggested that the synthesized films have a cubic ThZr2H7 crystal structure with AgBi2I7 stoichiometry. Through careful examination of the proposed structure and computational evaluation of the phase stability and bandgap, we find that the reported "AgBi2I7" films cannot be forming with the ThZr2H7-type structure, but rather more likely adopt an Ag-deficient AgBiI4 type. Both the experimental X-ray diffraction pattern and bandgap can be better explained by the AgBiI4 structure. Additionally, the proposed AgBiI4 structure, with octahedral bismuth coordination, removes unphysically short Bi-I bonding within the [BiI8] hexahedra of the ThZr2I7 model. Our results provide critical insights for assessing the photovoltaic properties of AgBi2I7 iodobismuthate materials.

Bismuth‐Based Coordination Polymers with Efficient Aggregation‐Induced Phosphorescence and Reversible Mechanochromic Luminescence

AbstractTwo bismuth coordination polymers (CPs), (TBA)[BiBr4(bp4mo)] (TBA=tetrabutylammonium) and [BiBr3(bp4mo)2], which are based on the rarely used simple ditopic ligand N‐oxide‐4,4′‐bipyridine (bp4mo), show mechanochromic luminescence (MCL). High solid‐state phosphorescence quantum yields of up to 85 % were determined for (TBA)[BiBr4(bp4mo)] (λem=540 nm). Thorough investigations of the luminescence properties combined with DFT and TDDFT calculations revealed that the emission is due to aggregation‐induced phosphorescence (AIP). Upon grinding, both samples became amorphous, and their luminescence changed from yellow to orange and red, respectively. Heating or exposure to water vapor led to the recovery of the initial luminescence. These materials are the first examples of mechanochromic phosphors based on bismuth(III).

Bismuth‐Based Coordination Polymers with Efficient Aggregation‐Induced Phosphorescence and Reversible Mechanochromic Luminescence

Two bismuth coordination polymers (CPs), (TBA)[BiBr4 (bp4mo)] (TBA=tetrabutylammonium) and [BiBr3 (bp4mo)2 ], which are based on the rarely used simple ditopic ligand N-oxide-4,4'-bipyridine (bp4mo), show mechanochromic luminescence (MCL). High solid-state phosphorescence quantum yields of up to 85 % were determined for (TBA)[BiBr4 (bp4mo)] (λem =540 nm). Thorough investigations of the luminescence properties combined with DFT and TDDFT calculations revealed that the emission is due to aggregation-induced phosphorescence (AIP). Upon grinding, both samples became amorphous, and their luminescence changed from yellow to orange and red, respectively. Heating or exposure to water vapor led to the recovery of the initial luminescence. These materials are the first examples of mechanochromic phosphors based on bismuth(III).