Syntheses, crystal structure, and photoelectric properties of two Zn-based chalcogenidoantimonates Zn-Sb-Q (Q = S, Se).

Metal chalcogenides are a special class of semiconducting materials characterized by their rich structures and compositions, making them a promising option for a broad range of applications in the field of inorganic chemistry. However, the path forward is not without its challenges, notably in the realms of interface management and enhancing carrier concentration. To address these issues, we solvothermally synthesized two novel chalcogenidoantimonates [Zn(tren)]2Sb2Se5 (1) [tren = tris (2-aminoethyl) amine] and [Zn(tepa)H]2Sb2S6 (2) (tepa = tetraethylenepentamine) utilizing transition metal Zn by band gap optimization strategy in the visible region. Both compounds exhibited distinct zero-dimensional cluster structures, with transition metal complex cations acting as structure-directing agents. A comprehensive analysis of the electronic structure, band gap, and photocurrent response of these crystals was undertaken, revealing significantly enhanced photocatalytic properties compared to preceding studies. This research underscores the potential of antimony chalcogenides in the realm of photoelectric properties and promotes the applications of chalcogenides.

[3 + 2 + 1] Pyridine Skeleton Synthesis Using Acetonitrile as C4N1 Units and Solvent.

The first [3 + 2 + 1] methodology for pyridine skeleton synthesis via cascade carbopalladation/cyclization of acetonitrile, arylboronic acids, and aldehydes was developed. This reaction proceeds via six step tandem reaction sequences involving the carbopalladation reaction of acetonitrile, a nucleophilic addition, a condensation, an intramolecular Michael addition, cyclization, and aromatization. Delightfully, both palladium acetate and supported palladium nanoparticles catalyzed this reaction with similar catalytic performance. The characterization results of the fresh and used supported palladium nanoparticle catalysts indicated that the reaction might be performed via a Pd(0)/Pd(II) catalytic cycle that began with Pd(0). Furthermore, the products showed good fluorescence characteristics. The green homogeneous/heterogenous catalytic methodologies pave a new way for constructing the pyridine skeleton.

One pot synthesis of diarylfurans from aryl esters and PhI(OAc)2 via palladium-associated iodonium ylides.

The example of palladium-catalyzed intermolecular cyclization for the synthesis of various diarylfurans in which one of the aromatic rings originates from the phenolic part of the starting ester and the other one from PhI(OAc)2 has been reported. The reaction is carried out through two steps: the rearrangement of palladium-associated iodonium ylides to form o-iodo diaryl ether and then palladium catalyzed intramolecular direct arylation. This reaction can tolerate a variety of functional groups and is alternative or complementary to the previous methods for the synthesis of diarylfurans.

Energy-efficient green catalysis: supported gold nanoparticle-catalyzed aminolysis of esters with inert tertiary amines by C-O and C-N bond activations.

Catalyzed by supported gold nanoparticles, an aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of tertiary amides. Comparison studies indicated that the gold nanoparticles could perform energy-efficient green catalysis at room temperature, whereas Pd(OAc)2 could not.

Aminolysis of aryl ester using tertiary amine as amino donor via C-O and C-N bond activations.

An aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of a broad scope of tertiary amides under neutral and mild conditions. The mechanism may undergo the two key steps of oxidative addition of acyl C-O bond in parent ester and C-N bond cleavage of tertiary amine via an iminium-type intermediate.

Strong Photocurrent Response of Selenoarsenates With Different Transition Metal Complexes as Structure-Directing Agents.

Four selenoarsenates with different transition-metal complexes [Co(tren)2H]AsSe4 [tren = tris(2-aminoethyl)amine] (1); [Ni2(dien)4](As2Se5) (dien = diethylenetriamine) (2); [Zn(tren)]2(As2Se5) (3) and [Mn(tren)]2(As2Se5) (4) were solvothermally synthesized in a mixed solvent of organic amine and alcohol solution. The compounds 1-4 have pyramidal/tetrahedral structures (AsSe3/AsSe4), and contain transition metal (Co2+, Ni2+, Zn2+ and Mn2+) complex that form distinct zero-dimensional (0-D) clusters. Arsenic atoms form a tetrahedron in compounds 1 and 2; 1 consists of discrete tetrahedral (AsSe4) and transition metal complex [Co(tren)2]2+; 2 is composed of an anion [As2Se5]4- cluster and transition metal complex [Ni(dien)2]2+. In compounds 3 and 4, arsenic atom forms a pyramidal AsSe3 and the two pyramidal AsSe3 share a corner connection to form a dimer [As2Se5]4-; 3 is characterized as a cluster consisting of two unsaturated [Zn(tren)]2+ caiton linked by a dimer (As2Se5)4- linkage; in 4, unsaturated [Mn(tren)]2+ caiton is linked to two trigonal-bipyramidal [Mn(tren)]Se via dimer (As2Se5)4- to form [Mn(tren)]4[As4Se10] cluster. To our knowledge, [Zn(tren)]2(As2Se5) (3) is the first zinc selenoarsenate containing the (As2Se5)4- anion type. Furthermore, the Mn2+ ions adopt a trigonal-biyramidal (five-coordinate) and octahedral (six-coordinate) environment. Adding K2CO3/Cs2CO3 to the synthesis system is necessary and may act as a mineralizer. Several properties of compounds 1-4 have been characterized in our studies, in particular their strong photocurrent response characteristics under visible light irradiation.

Regiodivergent CDC reactions of aromatic aldehydes with unactivated arenes controlled by transient directing strategy.

The regiodivergent catalytic dehydrogenative cross-coupling reactions at both sp2 and sp3 hybridized carbons of aromatic compounds are particularly challenging. Herein, we report the finding of transient directing group controlled regiodivergent C(sp3)-C(sp2) and C(sp2)-C(sp2) cross-coupling in the o-methyl benzaldehyde frameworks. Catalyzed by palladium, using K2S2O8 or [F+] reagents as by-standing oxidants and unactivated arenes as substrates/solvents, various benzyl benzaldehydes or phenyl benzaldehydes were prepared. A mechanism study indicated that the regiospecificity is dominated by the [5,6]-fused palladacycle or [6,5]-fused palladacycle intermediates, which are generated from Pd-chelation with specified transient directing groups and further C-H activations.

The solvothermal synthesis and characterization of quaternary arsenic chalcogenides CsTMAsQ3 (TM = Hg, Cd; Q = S, Se) using Cs+ as a structure directing agent: from 1D anionic chains to 2D anionic layers.

Four new quaternary transition metal arsenic chalcogenide Cs-TM-As-Q compounds (TM = Hg, Cd; Q = S, Se) were synthesized using different mixed solvents. A 1,4-diaminobutane(1,4-dab)/water mixed solvent system was used to solvothermally synthesize the selenoarsenates CsTMAsSe3 (TM = Hg (1), Cd (2)). In 1, the eight-membered ring anion chain consists of trigonal-planar [HgSe3] and trigonal-pyramid [AsSe3]. Compound 2 is similar to the eight-membered ring chain anion of compound 1, and [CdAsSe3]- further joins, through µ3-Se and Cd, to form the layer anions [CdAsSe3]-. A 2-diaminopropane (1,2-dap) and water mixed solvent system was used to synthesize two thioarsenates, Cs2TM2As2S6 (TM = Cd (3), Hg (4)). Compounds 3, 4 and 2 are isostructural; the Cd and Hg atoms are four coordinated. Compounds 1-4 utilize Cs+ cations as a structural directing agent. Finally, the structural and optical properties of the novel series of arsenic chalcogenides were characterized.

Two Mercury Antimony Chalcogenides Cs2HgSb4S8 and Cs2Hg2Sb2Se6 with Cesium Cations as Counterions.

Two novel layer structure compounds, Cs2HgSb4S8 and Cs2Hg2Sb2Se6, were synthesized in organic solvent under solvothermal conditions. The Cs2HgSb4S8 is formed of [HgSb4S8]2- ribbons and S atoms by corner sharing. The Cs2Hg2Sb2Se6 is made up of [SbHg2Se6]5- ribbon and disorder trigonal-pyramidal SbSe3 by sharing µ3-Se. These compounds are characterized by single-crystal X-ray diffraction, powder X-ray diffraction, solid-state optical absorption spectra, and so on.

Transesterification of (hetero)aryl esters with phenols by an Earth-abundant metal catalyst.

Readily available and inexpensive Earth-abundant alkali metal species are used as efficient catalysts for the transesterification of aryl or heteroaryl esters with phenols which is a challenging and underdeveloped transformation. The simple conditions and the use of heterogeneous alkali metal catalyst make this protocol very environmentally friendly and practical. This reaction fills in the missing part in transesterification reaction of phenols and provides an efficient approach to aryl esters, which are widely used in the synthetic and pharmaceutical industry.

A solvothermal synthesis and the structure of K4Ag2Sn3S9 x 2KOH.

A novel layered K(4)Ag(2)Sn(3)S(9) x 2KOH was synthesized solvothermally. A mixture of ethanol and HSCH(2)CH(SH)CH(2)OH was used for the synthesis. The HSCH(2)CH(SH)CH(2)OH plays an important role and appears to serve as a mineralizer for the solvothermal reaction. A layer comprises Sn(3)S(9)(6)(-) clusters linked by Ag(+) ions and possesses two types of 1D channels in which potassium ions are located. The compound crystallizes in the monoclinic P2(1)/m space group [a = 7.8071(2) A, b = 27.3508(1) A, c = 10.5008(2) A, alpha = 90 degrees, beta = 103.874(1) degrees, gamma = 90 degrees, Z = 4]. Its crystal structure, composition analysis, and IR are presented.

K2Ag6Sn3S10: a quaternary sulfide composed of silver sulfide layers pillared by zigzag chains 1infinity[SnS3]2-.

A novel framework K(2)Ag(6)Sn(3)S(10) was synthesized solvothermally and characterized by single-crystal diffraction. The framework comprises [Ag(6)SnS(4)](2+) cationic layers pillared by [SnS(3)](2)(-) zigzag chains formed by vertex-sharing SnS(4) tetrahedra, and potassium ions are located in 1D channels. This compound crystallizes in the orthorhombic Pbcn space group with a = 24.0201(2) A, b = 6.4017(3) A, c = 13.3056(4) A, Z = 4. Its thermal and optical properties are studied.