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The novel iron selenidostannates [Fe(bipy)3]Sn4Se9·2H2O (1) and [Fe(bipy)3]2[Sn3Se7]2·bipy·2H2O (2) (bipy = bipyridine) were prepared by the reactions of Sn, Se, FeCl2·4H2O, bipy, and dien with/without KSCN under hydrothermal conditions (dien = diethylenetriamine). In 1, four SnSe5 units condense via edge sharing to form the novel 3-D framework selenidostannate ∞³[Sn4Se92-] 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 2, three SnSe5 units share edges to form a 2-D ∞²[Sn3Se72-] layered anion, while two SnSe5 units and one SnSe4 unit are connected via edge sharing, forming a 1-D ∞¹[Sn3Se72-] chainlike anion. The ∞¹[Sn3Se72-], [Fe(bipy)3]2+, bipy, and H2O species are embedded between the ∞²[Sn3Se72-] layers. 2 is the first example of a selenidostannate constructed by both ∞²[Sn3Se72-]and ∞¹[Sn3Se72-] anions. The coexistence of 1-D ∞¹[Sn3Se72-] and 2-D ∞²[Sn3Se72-] anions in 2 might support the possible reaction mechanism that the ∞²[Sn3Se72-] anions are formed by condensation of the ∞¹[Sn3Se72-] chains. 1 and 2 exhibit band gaps at 1.43 and 2.01 eV, respectively [ABSTRACT FROM AUTHOR]

Novel heterometallic Ag-iodoplumbates [Ln(DMSO)8]Pb2Ag2I9 [Ln = La(1), Gd(2), Tm(3)] were prepared by reactions of LnCl3, PbI2, AgNO3 and KI in dimethyl sulfoxide (DMSO). The same reactions without reactant AgNO3 produced new iodoplumbates [Ln(DMSO)8][(DMSO)Pb4I11] [Ln = La(4), Pr(5), Nd(6)]. All Ln3+ ions are solvated with eight DMSO molecules in the reactions, forming [Ln(DMSO)8]3+ complex cations to act as counterions to the iodometallate anions. In compounds 1-3, two AgI4 tetrahedra and two PbI6 octahedra are connected into the 1D heterometallic Ag-Pb iodometallate [Ag2Pb2I9]n 3n- via face-sharing. The [Ag2Pb2I9]n 3n- anionic chains run parallel along the b axis in 1, and along the a axis in 2 and 3. The [Ln(DMSO)8]3+ cations are located between the chains. In compounds 4-6, two PbI6 and two PbI5O octahedra are interlinked end to end via sharing common faces to generate a 1D [(DMSO)Pb4I11]n 3n- chain, which represents a new member of iodoplumbate aggregates. In the [(DMSO)Pb4I11]n 3n- chain, the Pb2+ ions are joined not only via μ-I bridges, but also via μ-O bridges. The μ-O oxygen bridging has never been observed in iodoplumbates. Solid state optical absorption spectral analyses show optical band gaps in the range of 2.25-2.88 eV for compounds 1-6. Blue shift of the absorption edge caused by copolymerization of the AgI4 unit occurs on the iodoplumbates. [ABSTRACT FROM AUTHOR]

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] (1) and [Ni(dien)2][Ni(As3S3)2] (2) (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] (3) (en = ethylenediamine). In 1 and 2, 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 duster, in which TMAS², TMAs2S2, and TMAs3S2 rings are formed. In 3, each Co3+ ion is coordinated by an en ligand. Six Co(en) units are interlinked by four //3-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 n¹-AS11n²-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 1--3 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 (4) and [Co(en)3]2As2S5 (5) containing discrete anions [As3S6]3- and [As2Ss]4-, respectively. The band gaps of 1--3 are in the range of 1.37--1.55 eV, and die band gaps of 4 and 5 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. [ABSTRACT FROM AUTHOR]

Hybrid organic-inorganic Pb-Ag heterometallic iodides [(en)2(PbAgI3)]2n·nH2O (1), [(pda)2(PbAgI3)]n (2), [(tmeda)(PbAgI3)]n (3), [(trien)(PbAgI3)]n (4), [(tepa)(PbAg2I4)]n (5), and [{(dien)3(CO3)}2(Pb6Ag8I15)]nIn (6) were prepared by the reactions of PbI2, AgI (or Ag2CO3) and KI with different polyamines in N,N'-dimethylformamide (DMF) solution. In 1-4, two AgI4 tetrahedra share a common edge to form the bimeric Ag2I6 unit. It coordinates to the Pb(II) ion of [PbL2]2+ or [PbL']2+ (L = en, pda; L' = tmeda, trien) via iodine atoms to form hybrid organic-inorganic heterometallic iodides 1, 2, 3 and 4, respectively. Compounds 1, 3, and 4 contain 2-D layered backbones of [PbAgI3]n, whereas 2 contains a backbone of [PbAgI3]n with a 3-D structure. Steric hindrance and denticity of the ethylene polyamines influence the coordination modes and connection strength between the iodoargentate aggregates and Pb(II) ions. In 5, the AgI4 units are joined via sharing common edges to form a 1-D polymeric [Ag2I4]n2n- anion. It is connected with [Pb(tepa)]2+via iodine atoms to form a 3-D network of [(tepa)(PbAg2I4)]n. In 6, the CO32- ion binds three [Pb(dien)]2+ units to form the novel trinuclear [{Pb(dien)}3(µ3-CO3)]4+ complex ion. Eight AgI4 tetrahedra are connected via sharing common edges to give a novel Ag8I15 cluster with C3 symmetry. The Ag8I15 cluster and the [{Pb(dien)}3(CO3)]4+ unit are connected to form a novel layered heterometallic iodometallate cation [{(dien)3(CO3)}2(Pb6Ag8I15)]nn+via sharing iodine atoms. Compounds 1-6 represent a new type of hybrid organic-inorganic heterometallic iodide containing coordinative organic components. Optical absorption spectra show a blue shift of the absorption edges for 1-6 compared with those of the bulk PbI2 and AgI solids. [ABSTRACT FROM AUTHOR]

The iron selenidoantimonate(III) [Fe(phen)3]Sb6Se10 ( 1) (phen = 1, 10-phenanthroline) was prepared by reaction of Fe, Sb, Se, phen, and 1, 4-diazabicyclo[2.2.2]octane in MeOH and H2O mixed solvent under solvothermal conditions. 1 consists of a [Fe(phen)3]2+ cation and a two dimensional [Sb6Se10]2- anion. The [Sb6Se10]2- anion is constructed by SbSe3, SbSe4, and SbSe6 primary building blocks by corner- and edge-sharing, resulting Sb4Se4, Sb5Se5, and Sb6Se6 heterorings and a semi-cubic Sb4Se6 motif, which act as secondary building units. The octahedral SbSe6 primary unit and semi-cubic Sb4Se6 motif make compound 1 quite different from the thioantimonates(III). Compound 1 exhibits steep bandgap ( Eg) of 1.56 eV, indicating potential semiconducting property. The thermal stability of 1 was also investigated. [ABSTRACT FROM AUTHOR]