Dalton Transactions

PAPER The formation of title complexes shows the effects of lanthanide metal size and amino ligand denticity on the lanthanide selenidostannates. Complexes 1a-2c exhibit semiconducting properties with band gaps between 2.08 and 2.48 eV

Clusters [Co(As₃S₃)₂]^2–, [Ni(As₃S₃)₂]^2–, and [{Co(en)}₆(μ₃‑S)₄(AsS₃)₄]^2– with Co–As or Ni–As Bonds: Solvothermal Syntheses and Characterizations of Thioarsenates Containing Transition-Metal Complexes

Solvothermal reactions of As₂O₃ and S with CoCl₂·6H₂O or NiCl₂·6H₂O in an aqueous solution of dien produced novel thioarsenates [Co­(dien)₂]­[Co­(As₃S₃)₂] (<b>1</b>) and [Ni­(dien)₂]­[Ni­(As₃S₃)₂] (<b>2</b>) (dien = diethylenetriamine), and the reaction with CoCl₂·6H₂O in an aqueous solution of en afforded complex [Hen]₂[{Co­(en)}₆(μ₃-S)₄(AsS₃)₄] (<b>3</b>) (en = ethylenediamine). In <b>1</b> and <b>2</b>, one transition-metal ion is coordinated by two dien ligands to form [TM­(dien)₂]²⁺ (TM = Co, Ni) complex cations. The As₃S₃ unit coordinates to the other TM­(II) ion with both As- and S-donor atoms to form the [TM­(As₃S₃)₂]^2– anionic cluster, in which TMAs₂, TMAs₂S₂, and TMAs₃S₂ rings are formed. In <b>3</b>, each Co³⁺ ion is coordinated by an en ligand. Six Co­(en) units are interlinked by four μ₃-S and four AsS₃ ligands to form a [{Co­(en)}₆(μ₃-S)₄(AsS₃)₄]^2– cluster containing an adamantane-like Co₆S₄ core. The AsS₃ unit coordinates to Co atom in the η¹-As₁,η²-S coordination mode with As binding Co(1) and S(1) binding Co(1) and Co(2). The As₃S₃ and AsS₃ ligands with both As- and S-donor atoms in <b>1</b>–<b>3</b> have never been obtained in amine solution before. The same reactions in pure dien and en solvents afforded compounds [Co­(dien)₂]₃[As₃S₆]₂ (<b>4</b>) and [Co­(en)₃]₂As₂S₅ (<b>5</b>) containing discrete anions [As₃S₆]^3– and [As₂S₅]^4–, respectively. The band gaps of <b>1</b>–<b>3</b> are in the range of 1.37–1.55 eV, and the band gaps of <b>4</b> and <b>5</b> are 2.24 and 2.26 eV, which show the influence of the coordination mode of thioarsenate ligands on the electronic transitions in the TM-thioarsenates

Hydrazine-Assisted Syntheses and Properties of Mercury Tellurides Containing Transition-Metal Complexes

With assistance of reactive and coordinative hydrazine, transition-metal telluromercurates [Mn­(trien)­(N₂H₄)₂]₂­[Hg₂Te₄]₂ (<b>A</b>), [Zn­(trien)­(N₂H₄)₂]­Hg₂Te₄ (<b>B</b>), [Mn­(tepa)­(N₂H₄)]₂­Hg₄Te₁₂ (<b>C</b>), [TM­(trien)­(Hg₂Te₄)] (TM = Mn (<b>D</b>), Zn (<b>E</b>)), and [Zn­(atep)]₂Hg₅Te₁₂ (atep = 4-(2-aminoethyl)­triethylenetetramine) (<b>F</b>) were solvothermally prepared in triethylenetetramine (trien) or tetraethylenepentamine (tepa) solvents using elemental Te as precursor in lower temperature range. Compounds <b>A</b> and <b>B</b> consist of mixed coordination cations [TM­(trien)­(N₂H₄)₂]²⁺ (TM = Mn, Zn) and one-dimensional polyanion [Hg₂Te₄]^2– with the five-membered Hg₂Te₃ rings being coplanar. Compound <b>C</b> is composed of two [Mn­(tepa)­(N₂H₄)]²⁺ cations and a [Hg₄Te₁₂]^4– cluster with a centrosymmetric structure. Compounds <b>D</b> and <b>E</b> consist of coordination polymer [TM­(trien) (Hg₂Te₄)] containing novel doubled [Hg₂Te₄]_<i>n</i> chain with tetrahedrally coordinated Hg­(II) centers, which is quite different from the common single chain with the same composition of [Hg₂Te₄]_<i>n</i>. <b>D</b> and <b>E</b> are the first examples of telluromercurates incorporated with TM complex units via TM–Te bonds. Compound <b>F</b> contains fivefold coordinated [Zn­(atep)]²⁺ cations and zigzag [Hg₅Te₁₂^4–]_<i>n</i> polymeric anion. The [Hg₅Te₁₂^4–]_<i>n</i> anion is a new species of the binary telluromercurates. It is built from [Hg₄Te₆] and [HgTe₂(Te₄)] subunits via interconnectivity, which generates Hg₃Te₃ and Hg₄Te₄ rings in the structure. Compounds <b>A</b>–<b>F</b> are potential semiconductors with narrow band gaps in the range of 0.96–1.09 eV. Photocatalytic investigation of Mn­(II) complexes show that they are photocatalytically active in the degradation of CV under visible-light irradiation with the highest catalytic effective of cluster compound <b>C</b>

Novel One‑, Two‑, and Three-Dimensional Selenidostannates Templated by Iron(II) Complex Cation

The novel iron selenidostannates [Fe­(bipy)₃]­Sn₄Se₉·2H₂O (<b>1</b>) and [Fe­(bipy)₃]₂[Sn₃Se₇]₂·bipy·2H₂O (<b>2</b>) (bipy = bipyridine) were prepared by the reactions of Sn, Se, FeCl₂·4H₂O, bipy, and dien with/without KSCN under hydrothermal conditions (dien = diethylenetriamine). In <b>1</b>, four SnSe₅ units condense via edge sharing to form the novel 3-D framework selenidostannate _∞³[Sn₄Se₉^2–] containing an interpenetrating channel system. The [Fe­(bipy)₃]²⁺ cations are accommodated in the different channels according to the conformation of the [Fe­(bipy)₃]²⁺ cation. In <b>2</b>, three SnSe₅ units share edges to form a 2-D _∞²[Sn₃Se₇^2–] layered anion, while two SnSe₅ units and one SnSe₄ unit are connected via edge sharing, forming a 1-D _∞¹[Sn₃Se₇^2–] chainlike anion. The _∞¹[Sn₃Se₇^2–], [Fe­(bipy)₃]²⁺, bipy, and H₂O species are embedded between the _∞²[Sn₃Se₇^2–] layers. <b>2</b> is the first example of a selenidostannate constructed by both _∞²[Sn₃Se₇^2–]­and _∞¹[Sn₃Se₇^2–] anions. The coexistence of 1-D _∞¹[Sn₃Se₇^2–] and 2-D _∞²[Sn₃Se₇^2–] anions in <b>2</b> might support the possible reaction mechanism that the _∞²[Sn₃Se₇^2–] anions are formed by condensation of the _∞¹[Sn₃Se₇^2–] chains. <b>1</b> and <b>2</b> exhibit band gaps at 1.43 and 2.01 eV, respectively

Solvothermal syntheses and characterizations of polysulfido-thioantimonate and thioantimonate templated by Co-phen complex cation

<div><p>Polysulfido-thioantimonate [Co(phen)₃][Sb₄S₅(S₄)₂] (<b>1</b>), thioantimonates [Co(phen)₃]₂Sb₁₈S₂₉ (<b>2</b>), and [H₃O][Co(phen)₃]SbS₄·9H₂O (<b>3</b>) (phen = 1,10-phenanthroline) were prepared using [Co(phen)₃]²⁺ formed <i>in situ</i> as a structure directing agent in 80 and 50% CH₃OH aqueous solution or water solution, respectively. In <b>1</b>, eight Sb³⁺ ions are connected by ten μ-S²⁻ and four μ- bridging ligands to form a circular polysulfide thioantimonate anion [Sb₈S₁₀(S₄)₄]⁴⁻ which contains a sixteen-membered Sb₈S₈ heteroring. The Sb³⁺ ions are in trigonal pyramidal SbS₃ or trigonal bipyramidal <i>ψ</i>-SbS₄ geometries. In <b>2</b>, sixteen SbS₃ and two <i>ψ</i>-SbS₄ units are interconnected by sharing S atoms to form a 3-D [Sb₁₈S₂₉⁴⁻]_∞ framework containing an interpenetrating channel system, in which the [Co(phen)₃]²⁺ complexes are enclosed. In <b>3</b>, by O–H⋯O and O–H⋯S H-bonding, [SbS₄]³⁻,·H₂O and H₃O⁺ are interconnected into a anionic layer, which contains a (H₂O)₆ water cluster. The [Co(phen)₃]²⁺ complexes are located between the layers. The syntheses of <b>1</b>–<b>3</b> show the influences of different solvents on the Co/Sb/S/phen system. The optical band gaps of <b>1</b>–<b>3</b> are 2.02, 2.11, and 2.27 eV, respectively.</p></div