Chalcogens - Science topic

Density functional theory (DFT) driven by the quantum ESPRESSO code was used in this study to investigate the structural, opto-electronic, and thermoelectric properties of ternary perovskite chalcogenide compound. This is to examine their possible use in optoelectronics and reducing the dependency on silicon and fossil fuel. The Perovskite compound...

Compound 1 , (disulfane-1,2-diyl)bis( tert -butyldiisopropylphosphonium) bis[tetrachloridoaurate(III)], ( t Bu i Pr 2 P) 2 S 2 ·[AuCl 4 ] 2 , contains the first structurally characterized dication of the form {( R 3 P) 2 E } 2 ²⁺ . The ions are linked by S...Cl contacts and C—H methine ...Cl hydrogen bonds to form ribbons of residues parallel to th...

In this work, the vibrational spectra of magnesium monochalcogenide nanoparticles were examined numerically. The calculations were performed with Density Functional Theory and the examined magnesium monochalcogenide nanoparticles were formed from an initial cubic-like unit with type , where , after elongating this unit along one, two, and three ver...

In this work, the use of chalcogen bonding for the catalytic activation of trityl cation by chloride abstraction from bench stable trityl chloride and further application in C—C bond forming reactions is reported. In particular, telluronium salts bearing noncoordinative counter anions such as BArF24 proved highly efficient. Thus, low catalyst loadi...

Chemists have developed sophisticated structural monomers and meticulously regulated the strength and directionality of non‐covalent interactions to assemble a variety of novel supramolecular helices in accordance with the second strategy, resulting in significant research advancements. These investigations not only enhance our comprehension of the...

Ammonium oxathioamidate (1) was synthesised by the reaction between O-ethyl-thioxamate (oxalic acid-1-amide-2-O-ethyl ester) and ammonium hydrogen carbonate in water solution. Compound 1 was fully characterised by both microanalytical (elemental analysis, melting point determination) and spectroscopic means (FT-IR and NMR spectroscopy). Crystals su...

Silver chalcohalide antiperovskites (CAP), Ag$_{3}$XY (X = S, Se; Y = Br, I), are a family of highly anharmonic inorganic compounds with great potential for energy applications. However, a substantial and unresolved discrepancy exists between the optoelectronic properties predicted by theoretical first-principles methods and those measured experime...

Chalcogen bonding interactions have attracted significant attention in a broad chemistry community, with a particular focus on their ability to stabilise the key transition states in various organic synthetic routes. In this work, we demonstrate that they can also be harnessed in selective photoredox reactions, which cannot be otherwise achieved wi...

Treatment of [Cp*TiCl3] with [LiBH4 ⋅ THF] followed by thermolysis with [Ph2E2] (E=S or Se) resulted in the formation of classical diborane(6) complexes, [(Cp*Ti)(η⁴‐B2H4LL′)] (L=C6H4E; L′=C6H5E; 1 a: E=S, 1 b: E=Se), stabilized at titanium template. To the best of our knowledge, they are the first examples of mono‐metallic classical diborane(6) co...

Selenium disulfide (often referred to as SeS2) encompasses a family of mixed selenium-sulfide eight-membered rings, traditionally used as an anti-dandruff agent in shampoos. SeS2 can be produced by reacting hydrogen sulfide (H2S) with selenite (SeO32−) under acidic conditions. This chemistry is also possible with natural spring waters that are rich...

A novel strategy to catalyze alkylation reactions through chalcogen bond interaction using a supramolecular structure is presented herein. Utilizing just 1.0 mol % of selenoxide‐pillar[5]arene (P[5]SeO) as the catalyst we achieved efficient catalysis in the cyanation of benzyl bromide in water. Our approach demonstrated high efficiency and effectiv...

Nanoribbons (NRs) of atomic layer transition metal dichalcogenides (TMDs) can boost the rapidly emerging field of quantum materials owing to their width-dependent phases and electronic properties. However, the controllable downscaling of width by direct growth and the underlying mechanism remain elusive. Here, we demonstrate the vapor-liquid-solid...

The non‐covalent interactions in molecules play important roles towards their applications in various aspects such as molecular recognition, catalysis, supramolecular chemistry, structural biology, pharmacology etc. Interestingly, among various non‐bonding interactions, chalcogen bonding (ChB) has been extensively studied in different facets of cry...

The structural rigidity of tetrakis(4‐pyridyl)porphyrin (TPyP) has been utilised to prepare a robust novel porous coordination polymer of composition Cd2(TPyP)(sez)2 (TPyP=5,10,15,20‐tetra(4‐pyridyl)porphyrin, sez=1,2,5‐benzoselenadiazole‐5‐carboxylate). The coordination polymer may be described as a hexagonal porphyrin nanotube (PNT) and has the p...

Four functionalized BODIPY derivatives (BDP1 to BDP4) were synthesized and their optical properties investigated both in solution and when incorporated into a solid matrix. Recognizing the versatility of BODIPY derivatives and the increasing interest in developing new luminescent organic dyes embedded in polymers, the BODIPY derivatives were disper...

The efficient construction of chalcogen‐atom‐based chiral compounds remains a challenge, despite the importance of organoselenium and organosulfur compounds in life and materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report an en...

Organic luminescent radicals, unlike traditional closed‐shell fluorescent emitters, exhibit distinct luminescence mechanisms, offering promising potential for optoelectronic devices. To date, stable luminescent radicals have predominantly been confined to polychlorinated triphenylmethyl radicals, underscoring the need for new platforms to expand th...

An efficient catalytic system employing TMS•OTf for the regioselective thiolation of electron‐rich arenes with sulfonyl hydrazides has been developed. The reaction occurs in a solvent mixture of dichloroethane and trifluoroethanol under mild conditions, with the addition of water. This method furnishes a range of para‐thio‐substituted arenes and 3‐...

Chalcogen bond catalysis is a promising catalytic strategy, characterized by its environmental friendliness, relatively inexpensive cost, and similar reactivity to transition metal catalysis. Experimental results suggest that the S⋅⋅⋅π and Se⋅⋅⋅π bonds can efficiently drive the vinyl‐indole‐based Diels‐Alder reaction (Angew. Chem. Int. Ed. 2021, 60...

Crystals exhibiting glass-like and low lattice thermal conductivity ($\kappa_{\rm L}$) are not only scientifically intriguing but also practically valuable in various applications, including thermal barrier coatings, thermoelectric energy conversion, and thermal management. However, such unusual $\kappa_{\rm L}$ are typically observed only in compo...

Perovskite solar cells (PSCs) have been on the forefront of advanced research for over a decade, achieving constantly increasing power conversion efficiencies (PCEs), while their route towards commercialization is currently under intensive progress. Towards this target, there has been a turn to PSCs that employ a carbon electrode (C-PSCs) for the e...

Attaining superconducting critical temperatures (Tc) beyond the limit around 14 K observed thus far in spinel compounds AB2X4 (A, B = transition metals, X = O/chalcogen) could elucidate interaction intricacies and inform materials design. This work spotlights CuIr2S4, which exhibits a distinct metal-insulator transition below 230 K, as an unconvent...

The physicochemical properties of Mo-bearing transition-metal dichalcogenide (TMD) monolayers are critical to their catalytic potential. However, these properties are generally viewed as similar across monolayers, which limits their versatility and potential for synergy in processes such as the reduction reactions of carbon dioxide (CRR), nitrogen...

The synthesis of two‐dimensional transition metal dichalcogenide (2D‐TMD) materials gives rise to inherent defects, specifically chalcogen vacancies, due to thermodynamic equilibrium. Techniques such as chemical vapor deposition (CVD), metal‐organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), flux growth method, and mechanical...

Lewis acid/base‐free diarylgermanethione 3 and diarylgermaneselenone 4 were synthesized through reactions of a heteroleptic diarylgermylene with elemental sulfur and selenium, respectively. They were fully characterized by structural, spectroscopic and computational methods. Germanethione underwent 1,2‐addition with AlMe3 at the Ge=S double to give...

An operationally straightforward and highly efficient potassium tert‐butoxide facilitated protocol for the C‐3 chalcogenation of indolines under catalyst and additive‐free conditions has been established under ambient temperature. The salient features of the process include the development of transition metal‐free, oxidant‐free and iodine‐free, ato...

Photodynamic therapy (PDT) is widely accepted in medical practice for its targeted induction of apoptosis in cancerous cells. Angelicin (Ang) has traditionally been known for its efficacy in cancer treatment and its capability to enter a photoexcited triplet state. This study has comprehensively assessed the effects of substituting individual chalc...

Here, results on the tailored growth of monolayers (MLs) of transition metal dichalcogenides (TMDs) are presented using chemical vapor deposition (CVD) techniques. To enable reproducible growth, the flow of chalcogen precursors is controlled by Knudsen cells providing an advantage in comparison to the commonly used open crucible techniques. It is d...

Herein, we describe an electrochemical method for the synthesis of haloalkenyl chalcogenides from internal alkynes using hydrobromic and hydrochloric acids as halogenating agents, with the sole byproduct being hydrogen gas. This e‐halochalcogenation protocol generates electrophilic chalcogenium species under mild conditions in a simple, undivided c...

The N→C dative bond (DB), intramolecular chalcogen bond and π conjugation play important roles in determining the structures and properties of some molecular carbon materials and organic/polymeric photovoltaic materials. In this work, the interplay between the N→C DB, intramolecular chalcogen bond and π conjugation in the complexes formed by cyclo[...

The lanthanide contraction involves a reduction in atomic radius among f‐block elements below the expected level. A similar contraction is observed in group‐16 elements. The atomic radius of Se (117 pm) is slightly larger than that of S (104 pm) arising from the presence of d electrons, compared to the significant increase in atomic radius from O (...

A mechanochemical cross‐dehydrogenative coupling reaction of pyrazolones with thiols using ball milling is described. Benzeneselenol and dichalcogenide substrates are also compatible under mild reaction conditions, yielding up to 99 %. Notable features of this reaction include its metal‐ and solvent‐free, wide substrate scope and good functional gr...

The density functional theory is used to investigate the complex relationships between the physical properties of the novel quaternary SrScCu3M4 (M = Se, Te) semiconductors. The computed negative formation energy values of these materials demonstrate their stable nature. The distribution of ELF around chalcogens and Cu atoms shows substantial local...

The predilection of sp-, sp²-, and sp³-hybridized chalcogen-bearing molecules to engage in type I chalcogen···chalcogen interactions was comparatively unveiled in like···like/unlike CY···YC, YCY···YCY, and F2Y···YF2 (where Y = O, S, and Se) complexes, respectively. Upon the optimized monomers, a potential energy surface (PES) scan was conducted to...

The rare-earth chalcogenide $ARECh_{2}$ family ($A =$ alkali metal or monovalent ions, $RE =$ rare earth, $Ch =$ chalcogen) has emerged as a paradigmatic platform for studying frustrated magnetism on a triangular lattice. The family members exhibit a variety of ground states, from quantum spin liquid to exotic ordered phases, providing fascinating...

Recently reported van der Waals layered honeycomb rare-earth chalcohalides REChX (RE = rare earth, Ch = chalcogen, and X = halogen) are considered to be promising Kitaev spin liquid (KSL) candidates. The high-quality single crystals of YbOCl, a representative member of the family with an effective spin of 1/2, are available now. The crystalline ele...

Chalcogens are used as sensitive redox‐responsive reagents in tumor therapy. However, chalcogen bonds triggered by external ionizing radiation, rather than by internal environmental stimuli, enable site‐directed and real‐time drug degradation in target lesions. This approach helps to bypass chemoresistance and global systemic toxicity, presenting a...

Group 14/16 adamantane‐type hybrid clusters of the type [(RT)4E6] (T=group 14 element, E=group 16 element, R=organic group) have been reported to emit white‐light when irradiated in an amorphous state with a continuous‐wave (CW) infrared laser diode. This effect is enhanced if the cluster core is varied from a binary to a more complex composition....

Our interest in the design of heavy pnictogen‐based Lewis acids for anion trafficking across biological membrane mimics has led us to investigate trivalent bismuthenium cations as chloride anion transporters. Here, we describe two chlorodiarylbismuthines, elaborated on a peri‐substituted naphthalene backbone and stabilized by an adjacent thio‐ or s...

The formation of asymmetric microenvironments in proteins benefits from precise transportation of chirality across multiple levels through weak bonds in the folding and assembly process, which inspires the rational design and fabrication of artificial chiral materials. Herein, the chalcogen bonding‐directed precise transportation of supramolecular...

Tellurium is now recognized as a ‘technology-critical element’ that is quickly being used in innovative applications. The chemistry of organotellurium ligands has improved rapidly during the last three decades. Because of their enhanced accessibility and the possibility that they would display significantly different properties than their sulfur co...

N‐substituted pyridino‐based congeners of Ebselen, named here as Pyrselen, incorporating proximal Se and N atoms, undergo dimerization in solution and the solid state through a dual donor‐acceptor arrangement of chalcogen bonding sites. Dimerization constants were measured within the 5–50 M⁻¹ range. Computational studies on the dimers depict a nota...

Determining ion‐pair affinities in heteroditopic receptor systems presents a persistent and significant challenge. The plethora of technical and experimental problems implicated in measuring ion‐pair affinities have encouraged the use of several expedient experimental practices as a means of characterising ion‐pair recognition behaviour. Exploiting...

In recent times, diaryliodonium reagents (DAIRs) have witnessed a resurgence as arylating reagents, especially under photoinduced conditions. However, reactions proceeding through electron donor‐acceptor (EDA) complex formation with DAIRs are restricted to electron‐rich reacting partners serving as donors due to the well‐known cage effect. We disco...

Doping polycyclic aromatic hydrocarbons with heteroatoms enables manipulation of their electronic structures. Herein, the structures and properties of phosphorus (P) doped heterosumanenes (HSEs) are regulated by varying the valence states of P‐dopant. The phosphine sulfide (PV) and chalcogens (S, Se, Te) co‐doped HSEs (1‐3) are reduced to trivalent...

Integration of spirocycles with buckybowls is a promising strategy to construct three‐dimensional (3D) curved π‐systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon‐bridged spiro‐type heterosumanenes (spiro‐HSEs) were synthesized by combining 9,9′‐spirobifluorene and dichalcogenasumanenes (DC...

Selenium has reemerged as a promising absorber material for tandem and indoor photovoltaic (PV) devices due to its elemental simplicity, unique structural features, and wide band gap. However, despite rapid recent improvements, record Se solar cells only reach a third of their achievable efficiencies at the radiative limit, primarily due to a low o...

The mercury(II) halide complex [1,3-di- tert -butyl-2,4-bis( tert -butylamino)-1,3,2λ ⁵ ,4λ ⁵ -diazadiphosphetidine-2,4-diselone-κ ² Se , Se ′]diiodidomercury(II) N , N -dimethylformamide monosolvate, [HgI 2 (C 16 H 38 N 4 P 2 Se 2 )]·C 3 H 7 NO or ( 1 )HgI 2 , 2 , containing cis -[( t BuNH)(Se)P(μ-N t Bu) 2 P(Se)(NH t Bu)] ( 1 ) was synthesized an...

MXenes are a diverse family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides. They can be synthesized through both top-down approaches, such as selective etching of A-layers from MAX phases using acids or molten salts, and bottom-up approaches, such as direct synthesis using chemical vapor deposition. However, the degr...

Six‐vertex closo‐SB5Cl5 (1) and ten‐vertex closo‐1‐SB9Cl9 (2) thiaboranes have been prepared, besides the already known 12‐vertex closo‐SB11Cl11 (3), from the co‐pyrolysis reaction of B2Cl4 with S2Cl2 at 280 °C in vacuo. The compounds are sublimable, off‐white solids. Their elemental composition has been determined by high‐resolution mass spectrome...

During our studies of the oxidation of gold(I) complexes of tri­alkyl­phosphane chalcogenides, general formula R¹R²R³PEAuX, (R = tert-butyl or isopropyl, E = S or Se, X = Cl or Br) with PhICl2 or elemental bromine, we have isolated a set of seven mixed-valence by-products, the bis­(tri­alkyl­phosphane chalcogenido)gold(I) tetra­halogenidoaurates(II...

We analyze the adsorption and ring‐opening reaction of pentacyclic chalcogen alkyls with chalcogen atoms ranging from oxygen to tellurium using computational analysis. Thus extends our previous investigation of THF on silicon towards germanium surface and towards the heavier chalcogen homologues. We found an increasing dative bond strength of the p...

A new pyridine-fused seleno­diazo­lium salt, 3-(phenyl­selan­yl)[1,2,4]selena­diazolo[4,5-a]pyridin-4-ylium chloride di­chloro­methane 0.352-solvate, C12H9N2Se2⁺·Cl⁻·0.352CH2Cl2, was obtained from the reaction between 2-pyridyl­selenenyl chloride and phenyl­seleno­cyanate. Single-crystal structural analysis revealed the presence of C—H⋯N, C—H⋯Cl⁻,...

Electron distribution and bonding in extended structures based on square planar gold complexes, traditionally classified as gold (III), have been addressed through solid‐state DFT calculations. The band structure analysis, taken as a diagnostic tool, highlighted that, when the metal is associated with chalcogen atoms, the gold centers are more elec...

The electronic, optical, and thermoelectric properties of the pure and (S, Se, and Te)-doped into the oxygen site of LaAlO3 and KNbO3 compounds have been investigated using the Locale Density Approximation with modified Becke and Johnson, based on the density functional theory. These doped structures represent p-type semiconductors with a direct ba...