Halide Substitution Research Articles

Cover Picture: Enhancing the Supercapacitive Behaviour of Cobalt Layered Hydroxides by 3D Structuring and Halide Substitution (Batteries & Supercaps 11/2024)

Cover Picture: Enhancing the Supercapacitive Behaviour of Cobalt Layered Hydroxides by 3D Structuring and Halide Substitution (Batteries & Supercaps 11/2024)

One‐Pot Synthesis of 2,4,6‐Trialkoxy‐ and Triaryloxybenzoates by Cs2CO3‐Mediated Tandem Dimerization/(3+3) Cyclocondensation of 1,3‐Acetonedicarboxylates

AbstractIn this study, Cs2CO3‐mediated one‐pot tandem dimerization/(3+3) cyclocondensation of 1,3‐acetonedicarboxylates followed by substitution of alkyl or aryl halides was developed to construct functionalized 2,4,6‐trialkoxy‐ and triaryloxybenzoates. In the effective reaction, the core benzene system was formed in a single‐step process under open‐vessel conditions. A plausible mechanism for this reaction is proposed and discussed herein.

Histidine-based hybrid perovskites as promising materials for wide wavelength photodetection

Layered 2D hybrid organic-inorganic perovskites (2D-HOIPs) exhibit a distinctive array of properties, including remarkable structural flexibility, enhanced resistance to moisture, and optoelectronic characteristics valuable for practical applications. Consequently, these materials are now widely acknowledged as pivotal components in optical and optoelectronic technologies. However, a significant drawback of 2D-HOIPs is their wide band gaps that has hindered their widespread application in optoelectronic devices. In this work we address this limitation by offering a novel series of 2D mixed-halide tin-based HOIPs with general formula (L-HisH)2SnBrxI4−x (where L-His = L-histidine, x = 4, 3.37, 1.70, 0.56, 0.44, and 0) for which the band gap can reach record narrow values, which are not typical for 2D-HOIPs. These compounds can be easily obtained in wide compositional range by implementing halide substitution approach. Each hybrid perovskite features a chiral structure imparted by chiral L-histidinium(+) cations interleaved between corner-shared tin halide octahedra, organized into single-layer thin inorganic slabs. Crucially, these new materials provide a high degree of flexibility in tuning their band gaps throughout the entire visible light spectrum, encompassing a range between 1.82 and 3.05 eV. As a “proof-of-concept”, we created a prototype HOIPs photodetector in which this HOIP was used as an active layer. It is noteworthy that the band gap of pure iodide perovskite is surprisingly narrow for this class of materials. The production of semiconductor materials with a variable width of the optical bandgap is the key to more versatile and diverse applications of these materials in the active components of modern optoelectronic devices. For the obtained prototype, light detection is observed in the wide range covering UV, visible and near-IR regions, marking a record achievement for 2D-HOIPs. Beyond photodetectors, these new histidine-based perovskites hold promise for applications in various other optoelectronic devices, including solar cells, photodiodes, phototransistors, polarized light detectors, and more.

Semisynthetic Studies Establish a Role for Conjugate Halide Exchange in the Formation of Chlorinated Pyrroloiminoquinones and Related Alkaloids.

Two novel pyrroloiminoquinone alkaloids, 6-chlorodamirone A and 6-bromodamirone A, have been identified for the first time from the marine sponge Latrunculia sp. (order: Poecilosclerida: family Latrunculiidae), sourced from Western Australia. Alongside these new compounds, seven previously known metabolites were also isolated. Despite being obtained in submilligram quantities, the structures of these natural products were successfully elucidated using high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy. To confirm the structures of these newly discovered alkaloids, a semisynthetic approach was employed starting from the more abundant metabolite, damirone A, additionally, single crystal X-ray crystallography was used to validate our structural proposals. The semisynthetic studies suggest that the chlorinated alkaloids are likely formed through a nonenzymatic conjugate halide substitution reaction rather than an enzymatic process. This reactivity parallels that observed in related metabolites, such as the caulibugulones B and C. Furthermore, a biomimetic cascade reaction was attempted to synthesize the spirodienone moiety characteristic of the discorhabdin alkaloids, inspired by the nucleophilic substitution observed in the tricyclic damirone A system. Albeit unsuccessful, these findings provide valuable insight into the reactivity of halogenated pyrroloiminoquinones under various conditions.

Enhancing the Supercapacitive Behaviour of Cobalt Layered Hydroxides by 3D Structuring and Halide Substitution

AbstractAmong the two‐dimensional (2D) materials, layered hydroxides (LHs) stand out due to their chemical versatility, allowing the modulation of physicochemical properties on demand. Specifically, LHs based on earth‐abundant elements represent promising phases as electrode materials for energy storage and conversion. However, these materials exhibit significant drawbacks, such as low conductivity and in‐plane packing that limits electrolyte diffusion. In this work, we explore the synthetic flexibility of α‐CoII hydroxides (Simonkolleite‐like structures) to overcome these limitations. We elucidate the growth mechanism of 3D flower‐like α‐CoII hydroxyhalides by using in situ SAXS experiments combined with thorough physicochemical, structural, and electrochemical characterization. Furthermore, we compared these findings with the most commonly employed Co‐based LHs: β‐Co(OH)₂ and CoAl layered double hydroxides. While α‐CoII LH phases inherently grow as 2D materials, the use of ethanol (EtOH) triggers the formation of 3D arrangements of these layers, which surpass their 2D analogues in capacitive behavior. Additionally, by taking advantage of their anion‐dependent bandgap, we demonstrate that substituting halides from chloride to iodide enhances capacitive behavior by more than 40 %. This finding confirms the role of halides in modulating the electronic properties of layered hydroxides, as supported by DFT+U calculations. Hence, this work provides fundamental insights into the 3D growth of α‐CoII LH and the critical influence of morphology and halide substitution on their electrochemical performance for energy storage applications.

Influence of Material Properties on Surface Chemistry Induced Circular Dichroism in Halide Perovskite: Computational Insights.

The chirality transfer phenomenon is attractive for enhancing the optical functionality of nanomaterials by inducing sensitivity to the circular polarization states of photons. An underexplored aspect is how material properties of the achiral semiconductor impact the induced chiroptical signatures. Here we apply atomistic time-dependent density functional theory simulations to investigate the material properties that influence the chiroptical signatures of a lead halide perovskite nanocrystal with a chiral molecule bound to the surface. First, we find that both lattice disorder created by surface strain and halide substitution can increase the chiroptical response of the perovskite quantum dots by an order of magnitude. Both phenomena are attributed to a broadening of the density of the electronically excited states. Second, the intensity of the anisotropy spectra decreases with increasing dot size with a power law decay. Overall, these insights can be used to help guide experimental realization of highly resolvable polarized optical features in semiconducting nanomaterials.

Photoluminescence Enhancement of 0D Organic-Inorganic Metal Halides via Aggregation-Induced Emission and Halide Substitution.

0D organic-inorganic metal halides (OIMHs) provide unprecedented versatility in structures and photoluminescence properties. Here, a series of bluish-white emissive 0D OIMHs, (TPE-TPP)2Sb2BrxCl8-x (x = 1.16 to 8), are prepared by assembling the 1-triphenylphosphonium-4-(1,2,2-triphenylethenyl)benzene cation (TPE-TPP)+ with antimony halides anions. Based on experimental characterizations and theoretical calculations, the emission of the 0D OIMHs are attributed to the fluorescence of the organic cations with aggregation-induced emission (AIE) properties. The 0D structure minimized the molecular motion and intermolecular interactions between (TPE-TPP)+ cations, effectively suppressing the non-radiative recombination processes. Consequently, the photoluminescence quantum efficiency (PLQE) of (TPE-TPP)2Sb2Br1.16Cl6.84 is significantly enhanced to 55.4% as compared to the organic salt (TPE-TPP)Br (20.5%). The PLQE of (TPE-TPP)2Sb2BrxCl8-x can also be readily manipulated by halide substitution, due to the competitive processes between non-radiative recombination on the inorganic moiety and the energy transfer from inorganic to organic. In addition, electrically driven light-emitting diodes (LEDs) are fabricated based on (TPE-TPP)2Sb2Br1.16Cl6.84 emitter, which exhibited bluish-white emission with a maximum external quantum efficiency (EQE) of 1.1% and luminance of 335cdm-2. This is the first report of electrically driven LED based on 0D OIMH with bluish-white emission.

The Study of Lead-Free CH3NH3GeX3 (X=F, Cl, Br, I and At) for Optoelectronic Applications Using First-Principle

Organometallic perovskites, with their exceptional electric, magnetic, piezoelectric, and optical properties, are prominent in materials science research. The environmental and health concerns associated with lead-based perovskites have spurred the search for lead-free alternatives, such as methylammonium germanium halides. This study investigates the optical and electronic properties of organometallic perovskite materials, focusing on methylammonium germanium halides (CH3NH3GeX3, where X = F, Cl, Br, I, At). Using computational methods, the analysed properties including band gap energies, dielectric constants, extinction coefficients, optical conductivity, absorption coefficients, reflectivity, refractive indices, and lattice constants. The results show a decreasing trend in band gap energies from 3.987 eV (CH3NH3GeF3) to 0.821 eV (CH3NH3GeAt3), indicating weaker bonding interactions with larger halide ions. Lattice constants increase from 4.981 Å (CH3NH3GeF3) to 6.068 Å (CH3NH3GeAt3), reflecting the larger ionic radii of the heavier halides. CH3NH3GeI3 displayed the highest dielectric constant, demonstrating a strong response to external electric fields. Extinction coefficients were significant within the 0 to 10 eV frequency range, with CH3NH3GeI3 showing the highest values. Optical conductivity peaked in CH3NH3GeI3, suggesting its potential for photovoltaic and light-emitting applications. The absorption coefficients indicated strong visible range absorption for CH3NH3GeI3. Reflectivity analysis revealed that CH3NH3GeF3 and CH3NH3GeCl3 had higher static reflectivity, suitable for applications requiring minimal reflection, whereas CH3NH3GeI3 exhibited minimal reflection, beneficial for high-efficiency photovoltaic cells. The refractive index analysis showed that CH3NH3GeI3 had the highest static refractive index, indicating significant optical density and light-slowing capabilities. These findings highlight the relationship between halide substitution and the optical properties of organometallic perovskite materials, providing insights for tailored technological applications.

Cooperative Catalytic Coupling of Benzyl Chlorides and Bromides with Electron-Deficient Alkenes.

Benzyl radicals are an important class of intermediate. The use of visible light to generate them directly from their respective halides is an ideal synthetic strategy. The central impediment associated with their direct single-electron reduction (photo- or electro-) lies in their highly variable and structurally dependent reduction potential, which combine to make the identification of a general set of conditions difficult. Herein, we have employed a strategy of nucleophilic cooperative catalysis in which catalytic lutidine undergoes halide substitution, which decreases and levels the reduction potential. This allows a general set of photocatalytic conditions to transform a broad range of benzyl halides into radicals that can be used in the synthesis of more complex molecules, exemplified here by Giese coupling with electron-deficient alkenes.

Nucleophilic Aromatic Substitution of Heteroaryl Halides with Thiols.

The nucleophilic aromatic substitution (SNAr) between heteroaryl halides (Cl, Br) and thiols proceeds smoothly in DMAc under the action of K2CO3 at rt-100 °C. For most electron-deficient heteroarenes, reaction takes place without introducing an additional electron-withdrawing group. For electron-rich heteroarenes, an additional electron-withdrawing group such as a simple ester, keto, cyano, and nitro group is required to ensure the reaction completes. The reactivity trend of heteroaryl halides is highly dependent on the electronic nature of the heteroarenes and orientation of halogens. Besides thiols, a couple of functionalized thioureas and thioamides are compatible with these conditions, providing the corresponding heteroaryl thioethers in good yields.

Expedient Synthesis of Alkyl and Aryl Thioethers Using Xanthates as Thiol-Free Reagents.

Thioethers are critical in the fields of pharmaceuticals and organic synthesis, but most of the methods for synthesis alkyl thioethers employ foul-smelling thiols as starting materials or generate them as by-products. Additionally, most thiols are air-sensitive and are easily oxidized to produce disulfides under atmospheric conditions; thus, a novel method for synthesizing thioethers is necessary. This paper reports a simple, effective, green method for synthesizing dialkyl or alkyl aryl thioether derivatives using odorless, stable, low-cost ROCS2K as a thiol surrogate. This transformation offers a broad substrate scope and good functional group tolerance with excellent selectivity. The reaction likely proceeds via xanthate intermediates, which can be readily generated via the nucleophilic substitution of alkyl halides or aryl halides with ROCS2K under transition-metal-free and base-free conditions.

Grubbs-Hoveyda catalysts conjugated to a β-barrel protein: Effect of halide substitution on aqueous olefin metathesis activity

The effect of halide substitution in Grubbs-Hoveyda II catalysts (GHII catalysts) embedded in the engineered β-barrel protein nitrobindin (NB4exp) on metathesis activity in aqueous media was studied. Maleimide tagged dibromido and diiodido derivates of the GHII catalyst were synthesized and covalently conjugated to NB4exp. The biohybrid catalysts were characterized spectroscopically confirming the structural integrity. When the two chloride substituents at ruthenium center were exchanged against bromide and iodide, the diiodo derivative was found to show significantly higher catalytic activity in ring-closing metathesis of α,ω-diolefins, whereas the dibromido derivative was less efficient when compared with the parent dichlorido catalyst. Using the diiodido catalyst, high turnover numbers of up to 75 were observed for ring-closing metathesis (RCM) yielding unsaturated six- and seven-membered N-heterocycles.

Exploring the Influence of Cation and Halide Substitution in the Structure and Optical Properties of CH3NH3NiCl3 Perovskite.

This manuscript details a comprehensive investigation into the synthesis, structural characterization, thermal stability, and optical properties of nickel-containing hybrid perovskites, namely CH3NH3NiCl3, CsNiCl3, and CH3NH3NiBrCl2. The focal point of this study is to unravel the intricate crystal structures, thermal behaviors, and optical characteristics of these materials, thereby elucidating their potential application in energy conversion and storage technologies. X-ray powder diffraction measurements confirm that CH3NH3NiCl3 adopts a crystal structure within the Cmcm space group, while CsNiCl3 is organized in the P63/mmc space group, as reported previously. Such structural diversity underscores the complex nature of these perovskites and their potential for tailored applications. Thermal analysis further reveals the stability of CH3NH3NiCl3 and CH3NH3NiBrCl2, which begin to decompose at 260 °C and 295 °C, respectively. The optical absorption properties of these perovskites studied by UV-VIS-NIR spectroscopy revealed the bands characteristic of Ni2+ ions in an octahedral environment. Notably, these absorption bands exhibit subtle shifts upon bromide substitution, suggesting that optical properties can be finely tuned through halide modification. Such tunability is paramount for the design and development of materials with specific optical requirements. By offering a detailed examination of these properties, the study lays the groundwork for future advancements in material science, particularly in the development of innovative materials for sustainable energy technologies.

Optoelectronic and transport properties of lead-free double perovskites Li2AgTlX6 (X = Cl, Br): A DFT study

Lead free double perovkistes is an emerging class of optoelectronic material which have a huge potential for futuristic electronic industry. In present communication, we theoretically studied the structural, optoelectronic, and thermoelectric properties of Li2AgTlCl6 and Li2AgTlBr6 using WIEN2k software. The permissible values of tolerance factor and enthalpy of formation ensure the structural and thermodynamic stability of these compositions. The substitution of halides increase the lattice constant from 10.52 to 11.11 Å and reduce the bulk modulus from 33.38 to 26.20 GPa. The calculation of Poisons and Pugh ratios ensures their ductile nature, whereas the examination of band structure indicates exposed the bansgap value of 2.0 and 1.2 eV for Li2AgTlCl6 and Li2AgTlBr6, respectively. A remarkable increase in optical parameters like static dielectric constant, refractive index, and shifting of peaks towards lower energy values is observed the replacement of Cl with Br. This substitution increased the electrical conductivity, specific heat at constant volume, Seebeck coefficient, and figure of merit that showed the feasibility of these compositions for photovoltaic and thermoelectric applications.

Deep insight into structural and optoelectronic properties of mixed anion perovskites

Abstract Here we present the optoelectronic properties of pure inorganic lead-free halide perovskites in the form of Cs2AgBiX 6 (X = Br, Cl, F, I) using the density functional theory calculations on cubic phase (Fm 3 ̅ m) and tetragonal phase (I4/m). First, all the structures of the two phases were optimized at the PBE level. Structural, electronic, optical properties, phonon, and thermal properties of Cs2AgBiX 6 in cubic (Fm 3 ̅ m) and tetragonal phases (I4/m) were obtained using the VASP code. Tetragonal phases of all compounds of the form Cs2AgBiX 6, except Cs2AgBiBr6, are reported here for the very first time. Among all the Cs2AgBiX 6 (X = F, Cl, Br, I) structures, the cubic phase of Cs2AgBiBr6 was seen to have the highest absorption coefficient along with prominent electronic features that are favorable for optoelectronic applications. Thus, the cubic phase of Cs2AgBiBr6 was selected as the host lattice and bromine atoms were partly replaced with chlorine and iodine atoms. Electronic and optical properties of these mixed halide compounds of Cs2AgBiBr6−xFx, Cs2AgBiBr6−xClx, and Cs2AgBiBr6−xIx where x = 1, 2, 3, 4, 5 are investigated with hybrid functional HSE06 level. The electronic structure revealed that these mixed compounds exhibited indirect band gap nature regardless of the halide substitution (different x concentration) and the band gap of Cs2AgBiBr6 could be varied with the substitutions of fluorine, chlorine, and iodine atoms. Our in-depth analysis shows that Cs2AgBiBr6 and their mixed halides have the potential to become active double perovskite materials for photovoltaic applications and as photocatalysts for water splitting.

Layered methylhydrazinium lead halide perovskites: new crystal polymorphs with a tailored band gap and photoluminescence colour via halide substitution

The Ruddlesden–Popper lead halide HOIPs exhibit rich temperature-driven polymorphism, bandgap adjustability, and shift of photoluminescence colour via the halide-mixing approach. This is the first report of a 3D perovskite phase with MHy+.

Halide-driven polarity tuning and optimized SHG-bandgap balance in (C4H11N2)ZnX3 (X = Cl, Br, I)

The halide substitutions in (C4H11N2)ZnX3 (X = Cl, Br, I) induce polarity tuning and then optimized SHG-bandgap balance.

Surefire generation of stannylpotassium: highly reactive stannyl anions and applications.

Organometallic reagents such as organolithium and Grignard reagents have long been esteemed in chemical synthesis for their exceptional reactivity. In contrast, the application of their sodium and potassium counterparts has been comparatively sluggish, notwithstanding their augmented reactivity stemming from their heightened ionic character. This inertia persists due to the constrained accessibility of these heavy alkali metal reagents. In this study, our focus was directed towards devising a convenient and pragmatic approach for fabricating heavy alkali metal-based reagents, particularly those grounded in potassium. Herein, we present a novel, direct method for generating stannylpotassium (Sn-K) reagents through the simple combination of readily available silylstannanes and t-BuOK. Subsequently, the generated Sn-K reagents were effectively harnessed for stannylative substitution of aryl halides, furnishing an array of arylstannanes straightforwardly under transition metal-free conditions. This application distinctly underscores the potential utility of highly reactive Sn-K species, hitherto sparingly tapped into within the realm of synthetic organic chemistry. Furthermore, our investigation confirms that Sn-K reagents manifest notably superior reactivity compared with their well-established stannyllithium (Sn-Li) counterparts. This heightened reactivity can be ascribed to the increasing ionic character of Sn-K, which was supported by computational experiments.

Diverse structural reactivity patterns of a POCOP ligand with coinage metals.

We have utilised the 4,6-di-tert-butyl resorcinol bis(diphenylphosphinite) (POCOP) ligand for exploring its coordination ability towards group 11 metal centres. The treatment of the bidentate ligand 1 with various coinage metal precursors afforded a wide range of structurally diverse complexes 2-12, depending upon the metal precursors used. This furnishes several multinuclear Cu(I) complexes with dimeric (2) and tetrameric cores (3, 4, and 5). The tetrameric stairstep complex 4 shows thermochromic behaviour, whereas the dimeric complex 2 and tetrameric complex 3 show luminescence properties at cryogenic temperatures. Interestingly, the halide substitution reaction of the dimeric complex 2 with KPPh2 produces a unique mixed phosphine-based tetrameric Cu(I) complex, 5. Treatment of the POCOP ligand with [CuBF4(CH3CN)4] in the presence of 2,2'-bipyridine afforded heteroleptic complex 6, consisting of tri- and tetra-coordinated cationic Cu(I) centres. Furthermore, we could also isolate cubane (8) and stairstep (9) complexes of Ag(I). The cationic Au(I) complex (12) was obtained from the dinuclear Au(I) complex of POCOP, 11. Complex 12 revealed the presence of a strong intramolecular aurophilic interaction with an Au⋯Au bond distance of 3.1143(9) Å. Subsequently, the photophysical properties of these complexes have been studied. All the complexes were characterised by single-crystal X-ray diffraction studies, routine NMR techniques, and mass spectroscopy.

Composition-dependent band structure parameters and band-gap bowing effect in a caesium lead mixed halide system: a cyclic voltammetry investigation.

Cyclic voltammetry techniques have been employed to study the effect of halide substitution on the band edge parameters and band gap bowing effect in the case of CsPbX3 [X = I, Br, Cl] perovskite nanocrystals (PNCs). A series of compositions, viz. CsPbI3, CsPb(I-Br)3, CsPbBr3, CsPb(Br-Cl)3 and CsPbCl3, have been prepared by a hot injection method. From powder XRD and HR-TEM analysis, the formation of a highly crystalline, cubic phase of the perovskite having size in the range from 7-20 nm has been confirmed. Sharp peaks in the photoluminescence spectra suggest the formation of quantum dots with narrow-size distribution. The composition-dependent optical band gap (εopgap) for CsPbX3 displays a systematic shift towards shorter wavelengths from I to Br to Cl substitutions. The cyclic voltammetry investigation on the dispersion of PNCs in nonaqueous solvents yielded prominent cathodic and anodic peaks. These are correlated to conduction (e1) and valence band edge (h1) positions, respectively. The h1 has been decreased substantially with I to Br to Cl in CsPbX3. Meanwhile, e1 shows a marginal increase. The values derived from CV data demonstrated an excellent match with UVPS results, reported for a similar system. From these results, the quasi-particle gap (εqpgap) and exciton binding energy have been estimated for all the compositions. The negative band gap bowing effect noted in these PNCs is attributed to the size quantization effect. The band-edge parameters reported in this work will be valuable in matching these heterojunctions with suitable electron/hole transport materials for optimum device-performance.