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Iodobismuthate hybrids [Ln(DMF)8][Bi2I9] (Ln = La (1), Eu (2)) and [Tb(DMF)8]2[Bi2I9]2 (3) were prepared using Ln(iii) complexes as SDAs. Compounds 2 and 3 exhibit high photocurrent density and effective catalytic activity in the photodegradation of CV and RhB.

New iodoargentate hybrids containing lanthanide complexes, [La(DMA)8]Ag9I12·2H2O (1) and [Ln(DMA)7]2Ag16I22 (Ln = Pr (2), Sm(3); DMA = N,N-dimethylacetamide), were prepared by diffusion methods using DMA-solvated lanthanide complexes as structure-directing agents. The octakis-solvated La3+ cation leads to formation of the 1-D nonanuclear [Ag9I12]n3n- polymeric anion constructed by AgI4 tetrahedral units through edge sharing, while the heptakis-solvated Ln3+ (Ln = Pr, Sm) cation affords the new 1-D hexadecanuclear [Ag16I22]n6n- polymeric anion built up from AgI4 units by both corner and edge sharing. Compounds 1-3 possess band gaps of 2.58, 2.77, and 2.74 eV, respectively, and show steady photocurrents in the range 14.2-18.0 μA under Xe light irradiation. They are photocatalytic active in the degradation of organic pollutants of crystal violet (CV) and rhodamine B (RhB) in water at room temperature. 2 and 3 perform higher photocatalytic activities than 1 in the CV degradation, which is attributed to the different photocurrent intensities. Photocatalytic mechanism investigations on compounds 2 and 3 show that h+ hole and ·O2- radical play major roles in the CV degradation, respectively.

New iodoplumbate hybrids with lanthanide complexes [La(DMF)8]Pb3I9 (1) and [Ln(DMF)8]Pb5I13 (Ln = Sm (2), Gd (3)) (DMF = N,N-dimethylformamide) were prepared using octakis complex cations [Ln(DMF)8]3+ formed in situ as structure directing agents by volatilizing at room temperature. The polymeric 1-D [Pb3I9]n3n− anion in compound 1 is constructed by PbI6 octahedral units via face-sharing featuring a waved chain structure, while the 1-D [Pb5I13]n3n− anion in 2 and 3 is composed of PbI6 units via both edge-sharing and face-sharing. The compounds 1–3 show steep band gaps at 3.02, 2.61, and 2.57 eV, respectively, indicating potential semiconducting properties. They exhibit catalytic activities in the photodegradation of organic pollutants like crystal violet (CV) and methylene blue (MB). Compounds 2 and 3 are more effective than 1 in the photocatalytic degradation of CV, which are related to their intensity of the photocurrent response. The photocurrent response, cyclic voltammetry measurements and photocatalytic mechanism investigation for compound 2 show that ˙OH radical and h+ hole are the main reactive species in the degradation experiment of CV.

By introducing copper(I) into Ln(NO3)3-PbI2-KI ternary system, three isostructural heterometallic iodoplumbates [Ln(DMSO)8][Pb2Cu2I9] (Ln = Pr (1), Sm (2), Gd (3)) (DMSO = dimethyl sulphoxide) have been prepared and structurally characterized. Compounds 1–3 contain 1D heterometallic Cu Pb iodometallate [Pb2Cu2I9]3− chains constructed by PbI6 and CuI4 units via edge and face-sharing. All Ln3+ ions are surrounded by eight DMSO molecules to form [Ln(DMSO)8]3+ complex cations acting as counterions to the iodometallate anions. Each [Pb2Cu2I9]n3n- anionic chain is surrounded by four arrays of the [Ln(DMSO)8]3+ complex cations. Their optical and thermal properties were investigated.

New Mn(II)-thioantimonate compounds [Mn(NH3)6]2[{Mn(NH3)3}2(μ3-SbS4)2]Cl2 (1), [Mn(NH3)6][{Mn(NH3)4}2(μ-SbS4)2]·2H2O (2), [Mn(NH3)6][{Mn2(μ-SbS4)2}(μ-N2H4)2] (3), and [{Mn(N2H4)}2{Mn(μ-SbS3)2(μ-N2H4)2}(μ-N2H4)2]n (4) were prepared in different hydrazine solution under solvothermal conditions. In 1, the tetrahedral SbS4 unit acts as a tridentate bridging ligand to connect the [Mn(NH3)3]2+ units into a 2-D lamellar anion [Mn(NH3)3(μ3-SbS4)2−]n containing 12-membered Mn3Sb3S6 heterorings. Two SbS4 ligands join two [Mn(NH3)4]2+ units with monodentate μ-1κ1S1: 2κ1S1 bridging mode, forming a binuclear [{Mn(NH3)4}2(μ-SbS4)2]2− anion in 2. In 3, the SbS4 ligand links [Mn2(μ-N2H4)2] units with tridentate bridging mode, to form a 1-D [{Mn2(μ-SbS4)2}(μ-N2H4)22−]n chain-like anion. Octahedral [Mn(NH3)6]2+ complex cation acts as the counter ion in compounds 1–3. In 4, the Mn(N2H4) units are interconnected into a neutral infinite [{Mn(N2H4)}2{Mn(μ-SbS3)2(μ-N2H4)2}(μ-N2H4)2]n chain by μ-SbS3 and μ-N2H4 bridging ligands. The trigonal pyramidal SbS3 unit adopts a tridentate bridging coordination mode μ-1κ2S1, S2:2κ2S1, S3. Compounds 1–4 exhibit tunable semiconducting band gaps varying in the range of 2.38–2.55 eV. Compounds 1 and 2 display higher photocatalytic activity in the degradation of crystal violet than in the degradation of methyl orange under visible light irradiation.

Diselenide-containing selenidostannates [TM(en)3]Sn3Se6(Se2) (TM = Mn (1), Fe (2), and Zn (3)) and [Ni(en)3]Sn3Se7.5 (4) (en = ethylenediamine) were prepared by the reactions of TMCl2, SnCl4·5H2O, Se and en in C2H5OH solvent under solvothermal conditions. The same reaction in C2H5OH/PEG-200 mixed solvent produced novel polyselenidostannates [TM(en)3][Sn(Se4)3] (TM = Mn (5), Fe (6), Zn (7), and Ni (8)). In 1–3, the interconnections of semi-cubic Sn3Se4 building units via four μ-Se2− and two μ-Se22− bridges give rise to the polymeric lamellar [Sn3Se6(Se2)]n2n− anion. The 1-D [Sn3Se7.5]n2n− anionic chain in 4 is built from the semi-cubic Sn3Se4 units interlinked by three μ-Se bridges and one μ-Se2 bridge at two Sn atoms with the third Sn atom being coordinated by a terminal Se2− anion. All the Sn4+ ions of [Sn3Se6(Se2)]n2n− are in five-fold coordination forming trigonal bipyramidal SnSe5 units, while both trigonal bipyramidal SnSe5 and tetrahedral SnSe4 units are observed in the 1-D [Sn3Se7.5]n2n− anion. In 5–8 the Sn4+ ion is chelated by three tetraselenide Se42− ligands, forming a [Sn(Se4)3]2− anion with the Sn4+ ion in an octahedral SnSe6 geometry. All the SnSe4 chelating rings of the [Sn(Se4)3]2− anion are in a half-chair conformation. The polymeric selenidostannates 1–4 are potential semiconductors with band gaps in the range of 2.04–2.18 eV. Compounds 5–8 have narrow band gaps between 1.55 eV and 1.74 eV, and exhibit distinct red shifts compared with the absorption edges of the layered selenidostannates 1–4. The manganese and iron compounds exhibit photocatalytic activities in the photodegradation of organic dye methylene blue (MB) under visible light irradiation at room temperature. The thermal decomposition residues of the manganese and iron compounds display higher catalytic activities than their precursors in the photodegradation of MB.

Organic-inorganic hybrid iodoplumbates [H2tmdp][PbI3]2∙DMF (1), [H2tmdp]2Pb7I18 (2), and [(H2tmdp)4(Hpyd)2(Me2NH2)][Pb6I22](I3)·2H2O (3) (tmdp = 4,4′-trimethylenedipiperidine, pyd = pyridine) were prepared using diammonium [H2tmdp]2+ as a structure directing agent under different conditions. The 1D [PbI3−]n polymeric anion in 1 is constructed by PbI6 octahedral units via face-sharing, while the 2D [Pb7I184−]n polymeric anion in 2 is composed of PbI6 units via both corner- and edge-sharing. The interconnection of PbI6 units via corner- and face-sharing generates a new iodoplumbate anion [Pb6I2210−]n in 3, featuring a waved layer structure. Compounds 1–3 exhibit steep band gaps at 2.32, 2.23, and 2.14 eV, respectively. Compounds 2 and 3 show photocatalytic activity in the degradation of methylene blue (MB) and rhodamine B (RhB) under visible light irradiation at room temperature. Compounds 1–3 are more effective in the photocatalytic degradation of MB than in the degradation of RhB.

Solvothermal reaction in tren/tatda mixed polyamines produced a transition metal (TM) thiostannate [Mn(tren)(H2O)][Mn(baen)]3Mn4Sn6S20∙9H2O (1) containing a novel T3 supertetrahedral nanocluster [Mn4Sn6S20]8−. The T3 cluster was constructed by SnS4 and MnS4 tetrahedra via corner-sharing with the SnS4 tetrahedra occupying four corners of the T3 cluster. It has different TM/Sn ratio from the traditional T3 cluster [TM5Sn5S20]10− (TM = Zn, Co) prepared by extraction method using alkali cations as the counter ions. Compound 1 is the first T3 cluster of the TM-Sn-Q phase prepared by solvothermal method and stabilized by TM-amino complex counter ions. The same solvothermal reaction with Se instead of S afforded a selenidostannate [Mn(baen)]2Sn2Se6 (2) containing a dimeric [Sn2Se6]4− anion. Compound 1 exhibits selective photocatalysis in photodegradation of organic dyes. It has higher photocatalytic effect in the photodegradation of crystal violet (CV) than rhodamine B (RhB) under visible light irradiation at room temperature.

Organic hybrid lanthanide(III) iodoargentates [Ln(DMSO)8]4Ag22I34·2H2O (Ln = La (1), Ce (2)), [Ln(DMSO)8]Ag7I10 (Ln = Eu (3), Tb (4), Dy (5)), and [Yb(DMSO)7]Ag5I8 (6) (DMSO = dimethyl sulphoxide) were synthesized by a diffusion method and structurally characterized. In 1 and 2, twenty AgI4 tetrahedra and two AgI3 triangles are connected via edge-sharing, forming the highly nuclear cluster [Ag22I34]12−. In 3–5, the 2D [Ag7I103−]n layer is constructed from Ag10I18 and Ag2I5 secondary building units via edge-sharing. The parallel packing of the [Ag7I103−]n layers generates channels with cross-sectional dimensions of 5.5 × 18.2 A2, in which the [Ln(DMSO)8]3+ counterions are trapped. In 6, three AgI4 and two AgI3 units are joined via corner- or edge-sharing to form the asymmetric structural unit Ag5I8. The Ag5I8 units are interconnected into a 1D [Ag5I83−]n chain via corner-sharing. The formation of [Ag22I34]12−, [Ag7I103−]n and [Ag5I83−]n anions indicates the different structure-directing effects of the Ln(III) ions across the lanthanide series. Compounds 3 and 4 display intense red and green luminescence at room temperature excited by 393 and 369 nm light, respectively.

Organic iodocuprate hybrids [dedabco]4(Cu4I8)2·H2O (dedabco = N,N'-diethyl-1,4-diazabicyclo[2.2.2]octane) (1), [H2tmdp]2(Cu2I5)(I)·H2O (tmdp = 4,4′-trimethylenedipiperidine) (2) and {[Hdbu]Cu2I3}n (dbu = 1,8-diazabicyclo-[5.4.0]-undec-7-ene) (3) were synthesized under solvothermal conditions using in-site formed organic cations as the structure directing agents. The tetrameric [Cu4I8]4– cluster in 1 is built up from four CuI4 units via edge-sharing, while the dimeric [Cu2I5]3– cluster in 2 is formed by two CuI4 units via face-sharing. The [Cu2I5]3– subunits are further interconnected by edge-sharing to generate 1-D polymeric [Cu2I3–]n anion in 3. The face-sharing CuI4 units causes short Cu∙∙∙Cu interactions in the [Cu2I5]3– and [Cu2I3–]n anions. Compounds 1–3 have narrow band gaps at 2.24 eV, 2.11 eV and 1.94 eV, and display steady photocurrent intensities of 0.13, 0.11, and 0.38nA under Xe light irradiation, respectively. Compound 3 performs higher photocatalytic efficiency in the degradation of crystal violet than compounds 1 and 2 due to its higher photocurrent intensitiy.

Organic silver-rich selenidostannate hybrid [H3dien][Ag5Sn4Se12]∙3H2O (1) was prepared in diethylenetriamine (dien) solvent under solvothermal conditions. In 1, the triangular AgSe3 and tetrahedral AgSe4 units are linked through corner-sharing to form a 1-D [Ag5Se8]n chain. Two SnSe4 tetrahedra are joined by sharing common edge forming a Sn2Se6 dimeric unit. Acting as a tetradentate linker, the Sn2Se6 unit connects the [Ag5Se8]n chains into polymeric 3-D [Ag5Sn4Se12]n3n− anionic framework, which contains 1-D channel with sectional dimensions of 7.339 A × 8.575 A. The dien and H2O molecules are enclosed in the channels. Compound 1 shows semiconducting properties with narrow band gap of 1.82 eV and strong photocurrent response with steady photocurrent intensity of 109 μA under Xe light irradiation. Compound 1 exhibits excellent photocatalytic effective in the photodegradation of MB under visible light irradiation at room temperature.

Two zinc binuclear complexes based on a hexaselenidobistannate bridging ligand, [{Zn(tren)}2(μ-Sn2Se6)] (1) and [{Zn(tepa)}2(μ-Sn2Se6)] (2) were prepared by solvothermal reactions of Zn, Sn, and Se in tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tepa) solvents, respectively. Compound 1 crystallizes in monoclinic space group C2/c, while 2 in tetragonal I4 1 /a. Acting as a bidentate bridging ligand, the bimeric [Sn2Se6]4− anion joins two [Zn(tren]2+ or two [Zn(tepa]2+ units via two trans terminal Se atoms to form the binuclear complexes 1 and 2, respectively. The Zn2+ ion is in a trigonal bipyramidal environment in 1 and in an octahedral environment in 2. Compounds 1 and 2 show well-defined absorption edges with band gaps of 2.38 and 2.31 eV at room temperature. New transition metal complexes base on hexaselenidobistannate ligand, [{Zn(tren)}2(μ-Sn2Se6)] and [{Zn(tepa)}2(μ-Sn2Se6)] were solvothermaly synthesized in tren and tepa (tren = tris(2-aminoethyl)amine, tepa = tetraethylenepentamine) solvents, respectively.

With assistance of reactive and coordinative hydrazine, transition-metal telluromercurates [Mn(trien)(N2H4)2]2[Hg2Te4]2 (A), [Zn(trien)(N2H4)2]Hg2Te4 (B), [Mn(tepa)(N2H4)]2Hg4Te12 (C), [TM(trien)(Hg2Te4)] (TM = Mn (D), Zn (E)), and [Zn(atep)]2Hg5Te12 (atep = 4-(2-aminoethyl)triethylenetetramine) (F) were solvothermally prepared in triethylenetetramine (trien) or tetraethylenepentamine (tepa) solvents using elemental Te as precursor in lower temperature range. Compounds A and 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 C is composed of two [Mn(tepa)(N2H4)]2+ cations and a [Hg4Te12]4– cluster with a centrosymmetric structure. Compounds D and E consist of coordination polymer [TM(trien) (Hg2Te4)] containing novel doubled [Hg2Te4]n chain with tetrahedrally coordinated Hg(II) centers, which is quite different from the common single chain with the same composition of [Hg2Te4]n. D ...

Four organic–inorganic hybrid selenidostannates, namely [H2en][H2dien][Fe(dien)2]2(Sn2Se6)2 (1), [Fe(dien)2]2Sn2Se6 (2), [Fe(dien)2]FeSnSe4 (3), and [Mn(dien)2]MnSnSe4 (4) (en = ethylenediamine; dien = diethylenetriamine), were prepared in different solvents under solvothermal conditions. Complexes 1 and 2 consist of discrete [Sn2Se6]4− and [Fe(dien)2]2+ ions, as well as organic cations [H2en]2+ and [H2dien]2+ in 1. The dimeric [Sn2Se6]4− anion is formed by two SnSe4 tetrahedra via edge-sharing. Complexes 3 and 4 are composed of one-dimensional polyanions [TMSnSe 4 2− ] n plus [TM(dien)2]2+ counter cations (TM = Fe, Mn). In the [TMSnSe 4 2− ] n anionic chain, the TM and Sn atoms are located at the same metal site with a ratio of 0.5/0.5. The TM1/2Sn1/2Se4 tetrahedra are interlinked via edge-sharing, forming the heterometallic [TMSnSe 4 2− ] n polymeric anion. The [TM(dien)2]2+ cations in 1–2 and 3–4 have u-fac and mer configurations, respectively. In all four crystal structures, the anions and cations are connected into extended structures via weak N–H···Se hydrogen bonds. The band gaps of complexes 1–4 calculated from the solid-state UV–vis diffuse reflectance spectra were at 2.58, 2.60, 2.21, and 2.25 eV, respectively. Thermogravimetric analyses show that complex 1 decomposes in three steps, while complexes 2–4 each decompose in one step.

New lanthanide-selenidostannate complexes [{La(peha)(Cl)}{La(peha)(NO3)}(μ-1κ2:2κ2-SnSe4)] (1), [H2trien][{La(trien)2}2(μ-1κ:2κ-Sn2Se6)][Sn2Se6]·H2O (2) and [{Ln(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)] n ·nH2O (Ln=Sm(3), Eu(4)) were prepared by solvothermal methods in pentaethylenehexamine (peha), triethylenetetramine (trien) and tetraethylenepentamine (tepa), respectively. Acting as a tetradentate chelating and bridging ligand, μ-1κ2:2κ2-SnSe4, the tetrahedral SnSe4 unit joins {La(peha)(Cl)}2+ and {La(peha)(NO3)}2+ complex fragments to generate the neutral coordination compound 1. The tetradentate μ-1κ2:2κ2 bridge in 1 represents a new coordination mode for the SnSe4 tetrahedron. In 2, dinuclear [Sn2Se6]4− anions are formed of SnSe4 tetrahedra via edge-sharing. One [Sn2Se6]4− anion acts as a bidentate bridging ligand in a μ-1κ:2κ coordination mode to join two {La(trien)2}3+ units, and the other [Sn2Se6]4− anion exists as a free charge compensating ion. In 3 and 4, the [Sn2Se6]4− anion connects binuclear [{Ln(tepa)(μ-OH)}2]2+ (Ln=Sm, Eu) units with a bidentate μ-1κ:2κ mode, giving neutral coordination polymers [{Ln(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)] n . The La(2)3+ ion in 1 is in a 10-fold coordination environment of LaN6O2Se2, whereas the La(1)3+ ions in 1 and 2 are in 9-fold coordinated environments forming polyhedra LaN6ClSe2 and LaN8Se, respectively. The Sm3+ and Eu3+ ions in 3 and 4 are both in an 8-fold coordination environment of LnN5O2Se. Compounds 1−4 exhibit optical band gaps between 2.21 and 2.42 eV. Their thermal stabilities were investigated by thermogravimetric analyses.

New selenidogermanate salts [NH 4] 2[H 2N(CH 3) 2] 2Ge 2Se 6 (1) and [Ni(dien) 2] 2Ge 2Se 5(Se 2) (2) (dien = diethylenetriamine), and a selenidogermanate complex [{Ni(tepa)} 2(μ-Ge 2Se 6)] (3) (tepa = tetraethylenepentamine) were prepared by solvothermal reactions. Compounds 1 and 2 consist of discrete [Ge 2Se 6] 4− and [Ge 2Se 7] 4− anions, and NH $_{4}^{+}$ , [H 2N(CH 3) 2] + and [Ni(dien) 2] 2+ counter cations, respectively. The [Ge 2Se 6] 4− anion is constructed by two tetrahedral GeSe 4 building units via edge-sharing. In 2, two tetrahedral GeSe 4 units are linked by a corner and a Se–Se bond to form a polyselenidogermanate anion [Ge 2Se 7] 4− containing a five-membered ring Ge 2Se 3. The dimeric [Ge 2Se 6] 4− anion acts as a bridging ligand via the trans terminal Se atoms to link two [Ni(tepa)] 2+ cations, resulting in neutral complex 3. The Ni 2+ ion in 2 is coordinated by two tridentate dien ligands, while it is coordinated by a pentadentate tepa ligand and a selenidogermanate anion in 3. The different coordination environments of Ni 2+ ions indicate the influence of the denticity of ethylene polyamines on the formation of selenidogermanates in the presence of transition metal ions. The compounds 1–3 exhibit optical band gaps between 2.06 and 2.35 eV.

New organic–inorganic hybrid selenidostannates [{Mn(2,2′-bipy)2}2(µ2-Sn2Se6)] (1) and [TM(2,2′-bipy)3]2[Sn3Se7]2·(2,2′-bipy)·H2O (TM = Co (2), Ni (3); 2,2′-bipy = 2,2′-bipyridine) were prepared under hydrothermal conditions. In 1, two edge-sharing [SnSe4] tetrahedra condense to form a dimeric [Sn2Se6]4– unit. The [Sn2Se6]4– unit is a tetradentate chelating ligand via four terminal Se atoms to join two unsaturated [Mn(2,2′-bipy)2]2+ complexes, forming a neutral complex [{Mn(2,2′-bipy)2}2(µ2-Sn2Se6)]. Compounds 2 and 3 consist of extended [Sn3Se7]2– selenidostannate anions, octahedral [TM(2,2′-bipy)3]2+ complex cations, and 2,2′-bipy and H2O molecules. The structural features of 2 and 3 are coexistence of both 1-D[Sn3Se72−]∞1 and 2-D[Sn3Se72−]∞2 polymeric anions. The 1-D[Sn3Se72−]∞1 chain is constructed by interconnection of the secondary building units (SBUs) Sn3Se9 via sharing two Se atoms, while the 2-D[Sn3Se72−]∞2 layer is constructed by Sn3Se10 SBUs via sharing three Se atoms. Compounds 1–3 exhibit narrow semiconducting band gaps varying in the range of 1.95–2.14 eV. Compound 2 displays higher photocatalytic activity than 1 on the degradation of crystal violet in water under visible irradiation.

Six new iodoargentates [Mn(2,2′-bipy)2(DMSO)2]Ag5I7 (1), [Mn(2,2′-bipy)2(DMF)2]Ag5I7 (2), [Zn(2,2′-bipy)2(DMF)2]Ag5I7 (3), [{Cd(2,2′-bipy)2}2(μ4-Ag2I6)] (4), [{Zn(DMF)2(H2O)2}(4,4′-bipy)1.5]Ag5I7·2DMF (5) and [Zn(4,4′-bipy)2(DMSO)2(H2O)2]Ag10I12·2DMSO·2H2O (6) (2,2′-bipy = 2,2′-bipyridine; 4,4′-bipy = 4,4′-bipyridine; DMF = N,N'-dimethylformamide; DMSO = dimethylsulfoxide) were prepared using transition metal complex cations as counter ions. The charge balance TM2+-2,2′-bipy (TM = Mn, Zn) complex cations modified by small ligands via solvating in different polar solvents lead to formation of γ-[Ag5I72−]n chains in compounds 1–3, while the [Cd(2,2′-bipy)2]2+ cation affords a binuclear neutral complex 4 which contains a novel tetradentate μ-Ag2I6 ligand. The solvated Zn2+-4,4′-bipy complex cation results β-[Ag5I72−]n and [Ag10I12]2– chain-like anions in 5 and 6, respectively. All the polymeric γ-[Ag5I72−]n, β-[Ag5I72−]n, μ-Ag2I6 and [Ag10I12]2– units are formed by the primary tetrahedral AgI4 units via corner- or edge-sharing. Compounds 1–6 show well-defined absorption edges with band gaps in the range of 2.68 to 2.86 eV at room temperature. Compounds 2 and 5 display higher catalytic activities than 4 in the photodegradation of organic dye CV. All ∙O2−, ·OH and h+ reactive species play an important role in the photodegradation of CV over compound 2, while ·OH are the main reactive species in the photocatalytic reaction using compound 5 as catalyst.

The first thione-protected cluster [Ag8(µ8-S)(mimt)12](NO3)6 (1) (mimt = 4-methyl-1,3-imidazolidine-2-thione) was synthesized by gradual S2– release from Na2S2O3 in solution and was structurally characterized. The cluster contains a novel octanuclear Ag8 cube that cages an S2– ion at the center, and the shell is stabilized by 12 µ2-mimt ligands. Each thione ligand bridges two Ag atoms to form the cubic edges. Cluster 1 exhibits luminescent emission in the solid state at 298 K with a maximum peak at 512 nm.

New lanthanide(III) compounds [[Ln(tepa)(Cl)]-[Ln(tepa)(OH)]2(SbSe4)2] n (Ln=Sm, Eu), [H2tepa][[Ln(tepa)(SbSe4)]2(OH)2] (Ln=Eu, Gd, Ho) (tepa=tetraethylenepentamine) were prepared by solvothermal methods. Acting as a bidentate μ-1κ:2κ-SbSe4 bridging ligand, the [SbSe4]3− unit interconnects [[Ln(tepa)]2(OH)2]4+ and [Ln(tepa)Cl]2+ (Ln=Sm, Eu) ions to form one-dimensional coordination polymers [[Ln(tepa)(Cl)][Ln(tepa)(OH)]2(SbSe4)2] n . The [SbSe4]3− unit acts as monodentate ligand to Ln(III) centers in [H2tepa][[Ln(tepa)(SbSe4)]2(OH)2]. The different coordination modes of the [SbSe4]3− units in [[Ln(tepa)(Cl)][Ln(tepa)(OH)]2(SbSe4)2] n and [H2tepa][[Ln(tepa)(SbSe4)]2(OH)2] are attributed to the size of Ln3+ ions. The bidentate μ-1κ:2κ-SbSe4 bridging ligand in [[Ln(tepa)(Cl)][Ln(tepa)(OH)]2(SbSe4)2] n is observed in the lanthanide complexes of tetraselenidoantimonate ligands for the first time. All compounds exhibit steep band gaps between 2.04 and 2.31 eV at room temperature.

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.

New members of transition metal complexes with thioarsenate ligands, [Co(peha)][Co(As 3 S 3 ) 2 ] (peha = pentaethylenehexamine) ( 1 ), [Co(trien)(AsS 3 )] ( 2 ), [Cr(trien)(AsS 3 )] (trien = triethylenetetramine) ( 3 ) and [Cr(en) 2 (AsS 3 )] (en = ethylenediamine) ( 4 ) were prepared by solvothermal reactions in polyamines. In 1 , two As 3 S 3 units coordinate to a Co 2+ ion with both As- and S-donor atoms in the 1κ 2 As 1 ,As 2 :1κS 1 -As 3 S 3 coordination mode to form the novel [Co(As 3 S 3 ) 2 ] 2− anionic cluster, in which CoAs 2 , CoAs 2 S 2 , and CoAs 3 S 2 rings are formed. Another Co 2+ ion is coordinated by a hexadentate peha ligand to form a octahedral [Co(peha)] 2+ complex cation. Both Co 3+ and Cr 3+ ions are coordinated by a tetradentate trien ligand and a bidentate chelating ligand [AsS 3 ] 3− , and neutral complexes [Co(trien)(AsS 3 )] ( 2 ) and [Cr(trien)(AsS 3 )] ( 3 ) are formed. The Cr 3+ is coordinated by two en ligands and a bidentate chelating ligand [AsS 3 ] 3− to form neutral complex Cr(en) 2 (AsS 3 )] ( 4 ). Complexes 2 – 4 represent the first examples of TM–thioarsenate complexes with polyethyleneamine coligands. Compounds 1 – 4 are potential semiconductors with narrow well-defined optical band gaps in the range of 1.45–1.74 eV. Thermal properties of 1 – 4 were investigated via thermogravimetric analyses.

Two lanthanide(III) complexes containing tetraselenidoantimonate ligand [Sm(peha)(μ-1κ 2 :2κ-SbSe 4 )] n ( 1 ), and [Eu(peha)(1κ 2 -SbSe 4 )] ( 2 ) (peha = pentaethylenehexamine) were solvothermally prepared by reactions Sb, Se and LnCl 3 in pentaethylenehexamine (peha). The tetrahedral [SbSe 4 ] 3 − unit connects [Sm(peha)] 3 + into the neutral 1-D coordination polymer 1 as a tridentate μ-1κ 2 :2κ-SbSe4 bridging and chelating ligand. It coordinates to [Eu(peha)] 3 + with a 1κ 2 -SbSe 4 chelating mode, forming the mononuclear complex 2 . The tridentate μ-1κ 2 :2κ-SbSe 4 bridging and chelating mode and 9-coordinate Sm(III) center in 1 are firstly observed in the systematic syntheses of the Sm/Sb/Se system in different polyethylenediamines. Compounds 1 and 2 exhibit steep band gaps at 2.04 and 2.11 eV at room temperature, respectively.

Polymeric lanthanide complexes with thiostannate and polyamine mixed ligands, [Ln(peha)(μ–SnS4H)]n [Ln=La (1a), Nd (1b)] and [{Ln(tepa)(μ–OH)}2(μ–Sn2S6)]nnH2O [Ln=Nd (2a), Sm (2b), Gd (2c), Dy (2d)] (peha=pentaethylenehexamine, tepa=tetraethylenepentamine) were respectively prepared in peha and tepa coordinative solvents by the solvothermal methods. In 1a and 1b, the Ln3+ ions are coordinated by a hexadentate peha ligand forming [Ln(peha)]3+ units. The [SnS4H]3− anion chelates a [Ln(peha)]3+ unit via two S atoms and coordinates to another [Ln(peha)]3+ unit via the third S atom. As a result, the [Ln(peha)]3+ units are connected into coordination polymers [Ln(peha)(μ–SnS4H)]n by an unprecedented tridentate μ–η1,η2–SnS4H bridging ligands. In 2a–2d, the Ln3+ ions are coordinated by a pentadentate tepa ligand, and two [Ln(tepa)]3+ units are joined by two μ–OH bridges to form a binuclear [{Ln(tepa)(μ–OH)}2]4+ unit. Behaving as a bidentate μ–η1, η1–Sn2S6 bridging ligand, the Sn2S6 unit connects [{Ln(tepa)(μ–OH)}2]4+ units into a neutral coordination polymer [{Ln(tepa)(μ–OH)}2(μ–Sn2S6)]n via the trans S atoms. The Ln3+ ions are in distorted monocapped square antiprismatic and bicapped trigonal prismatic environments in [{Ln(peha)(μ–SnS4H)]n and [{Ln(tepa)(μ–OH)}2(μ–Sn2S6)]n, respectively. The denticities of ethylene polyamine play an important role on the formation and complexation of the thiostannate in the presence of lanthanide ions. Compounds 1a–2d show well-defined absorption edges with band gaps between 2.81 and 3.15 eV.

A series of polymeric Mn(II)-thioarsenates [Mn(en)3]n[(N2H4)2Mn6(μ6-S)(μ-N2H4)2(μ3-AsS3)4]n (1), [N2H5]n[{Mn(μ-N2H4)2(μ-AsS4)}·0.5en]n (2), [Mn(μ-trien){Mn(μ-N2H4)(μ-AsS3)}2]n (3), [{Mn(N2H4)}2(μ-N2H4)2{Mn(μ-N2H4)2(μ-AsS3)2}]n (4), [Mn3(μ-N2H4)6(μ3-AsS4)(μ2-AsS4)]n (5), and [Mn(NH3)6]n[{Mn(NH3)(μ-AsS4)}2]n (6) were synthesized using a hydrazine-solvothermal method. The thioarsenate units AsS3 and AsS4 coordinate to Mn(II) ions with variable coordination modes, forming a Mn–As–S ternary cluster (1), chains (2, 4–6), and layers (3), respectively. The hydrazine molecules act as inter-cluster, intra-chain and intra-layer bridging ligands to join the Mn(II) ions, resulting in hydrazine hybrid 1-D, 2-D, and 3-D Mn(II)-thioarsenate moieties in 1–5. Compounds 1–6 exhibit tunable semiconducting band gaps varying in the range of 2.19–2.47 eV. Compound 1 displays stronger antiferromagnetic coupling interactions than that of compound 2.

New binuclear transition metal complexes concerning the bidentate S-donor ligand μ-Sn2S6, [{Mn(tren)}2(μ-Sn2S6)] (1), [{Zn(tren)}2(μ-Sn2S6)] (2), and [{Mn(tepa)}2(μ-Sn2S6)] (3) [tren = tris(2-aminoethyl)amine, tepa = tetraethylenepentamine] were prepared under methanolothermal conditions. The Mn2+ and Zn2+ ions are coordinated by a tren ligand, forming [TM(tren)]2+ (TM = Mn, Zn) units. As a bidentate bridging ligand, the hexathiobistannate [Sn2S6]4− anion joins two [TM(tren)]2+ units via trans terminal S atoms to form neutral complexes 1 and 2. Both Mn2+ and Zn2+ ions are in a trigonal bipyramidal environment. In 3, the Mn2+ ion binds a pentadentate tepa ligand to give a [Mn(tepa)]2+ unit. Two [Mn(tepa)]2+ units are connected by a μ-Sn2S6 bridging ligand, forming neutral complex [{Mn(tepa)}2(μ-Sn2S6)], in which the Mn2+ ion is in an octahedral environment. Intermolecular N–H···S H-bonding interactions connect 1–3 into layered structures, while 3 forms a three-dimensional network via the N–H···S H-bonds. 1–3 exhibit possible semiconducting properties with the band gaps at 2.3, 2.7 and 2.4 eV, respectively. Transition metal complexes concerning the bidentate S-donor ligand μ-Sn2S6, [{Mn(tren)}2(μ-Sn2S6)], [{Zn(tren)}2(μ-Sn2S6)], and [{Mn(tepa)}2(μ-Sn2S6)] were respectively synthesized using tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tepa) as second ligands under mild methanolothermal conditions.

Samarium selenidostannates [Hen][Sm(dien)3]Sn2Se6 (1), [Sm(trien)(tren)(Cl)]2Sn2Se6·0.5en (2), and [{Sm(en)(trien)}2(μ-OH)2]Sn2Se6 (3) (en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine, tren = tris(2-aminoethyl)amine) were prepared by solvothermal methods in mixed solvents of en/dien and en/trien, respectively. Compounds 1 and 2 consist of [Sn2Se6]4− anion and mononuclear Sm(III)-complex cations, and/or a protonated en and half a free en molecule. Compound 3 is composed of a [Sn2Se6]4− anion and a binuclear [{Sm(en)(trien)}2(μ-OH)2]4+ complex cation. As far as we know, 1–3 are the first examples of the lanthanide selenidostannates prepared in mixed ethylene polyamines. In the crystal structures of 1–3, the cations and anions are connected into three-dimensional supramolecular networks by N–H⋯Se and/or N–H⋯N, N–H⋯Cl and O–H⋯Se hydrogen bonds. Compounds 1–3 exhibit bandgaps in the range of 2.18–2.41 eV, and a distinct blue-shift of the bandgap from 2 to 1 and 3 is observed.

Two gadolinium selenidoantimonates [Gd(trien)2]SbSe4 (1) and [Gd(dien)(trien)(SbSe4)] (2) (trien = triethylenetetramine, dien = diethylenetriamine), were prepared by solvothermal reactions of Gd2O3, Sb and Se in trien and mixed trien + dien solvents respectively. Compounds 1 and 2 crystallize in monoclinic space group P21/c and P21/n, respectively. Cell Parameters of 1 are a = 9.2638(17), b = 13.462(3), c = 19.647(4) A, β = 92.776(3)°, V = 2,447.4(8) A3, Z = 4. Cell Parameters of 2 are a = 10.210(2), b = 17.602(4), c = 12.377(3) A, β = 90.280(5)°, V = 2,224.5(9) A3, Z = 4. In 1 the anion [SbSe4]3− exists as an isolated, charge-compensating anion for the [Gd(trien)2]3+ complex cation. It coordinates to the Gd(III) center of [Gd(dien)(trien)]3+ as a monodentate ligand to form a neutral mixed-coordinate complex [Gd(dien)(trien)(SbSe4)] (2). The coordination to Gd(III) center is influenced by the co-ligands of polyamines. New lanthanide selenidoantimonates [Gd(trien)2]SbSe4 and [Gd(trien)(dien)(SbSe4)] with 3-dimensional H-bonding network structures were respectively synthesized in trien and mixed trien/dien (trien = triethylenetetramine; dien = diethylenetriamine) solvents under mild solvothermal conditions.

The selenidostannates [Mn(dien)2]Sn3Se7·0.5H2O (1), [Fe(tatda)]Sn3Se7 (2), and [Mn(dien)2]2Sn2Se6 (3) (dien = diethylenetriamine, tatda = 3, 6,9, 12-tetraazatetradecane-1, 14-diamine) were prepared under solvothermal conditions. In compounds 1 and 2, the six Sn3Se4 semi-cubes are bridged by double μ2-Se atoms to form the [Sn3Se72–]n lamellar anion containing a elliptical 24-membered Sn12Se12 ring, which show conformational flexibility of the 2D [Sn3Se72–]n anion influenced by the counter cation. The [Mn(dien)2]2+ complex ion in 1 is in mer configuration. The [Fe(tatda)]2+ complex ion possesses similar configuration to the [Mn(dien)2]2+ ion in 1. The [Mn(dien)2]2+ and [Fe(tatda)]2+ cations are located between the [Sn3Se72–]n layers. Compound 3 consists of dimeric [Sn2Se6]4– anions and octahedral [Mn(dien)2]2+ complex cations with u-fac configuration. Compounds 1–3 have potential for uses as semiconductors with bandgaps in the range of 1.89–2.34 eV.

Ternary chromium selenidostannates [Cr(tepa)(OH)]2Sn2Se6·H2O (tepa = tetraethylenepentamine) (1) and [Cr(peha)]2(Sn2Se6)Cl2 (peha = pentaethylenehexamide) (2) were successfully synthesized by the reaction of CrCl3·6H2O, Sn, Se and tepa or peha in ionic liquid 1-ethyl-3-methylimidazolium chloride at 160 °C. In the ionic liquid, the Cr3 + ion forms [Cr(tepa)(OH)]2 + or [Cr(peha)]3 + chelating complex cations, which lead to the formation of chromium selenidostannates 1 and 2. But the reactions in pure tepa or peha under solvothermal conditions produced amorphous powders. 1 and 2 are the first examples of TM-complex contained chalcogenidostannates synthesized by ionothermal technique. Both 1 and 2 form three-dimensional networks via intermolecular N H⋯Se, O H⋯Se and N H⋯O or N H⋯Cl interactions, respectively. 1 and 2 exhibit possible semiconducting properties with the band gaps at 2.08 and 2.19 eV, respectively.

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.

Zinc tellurostannates [{Zn(teta)}2(μ-1κ:2κ-SnTe4)] (1), [{Zn(teta)}3(μ3-1κ:2κ:3κ-SnTe4)]I2 (2), [{Zn(tren)}2(μ-1κ:2κ-Sn2Te6)] (3), and [Zn(dien)2]4(Sn2Te6)1.75(Sn2Te8)0.25·dien (4) were prepared by the reactions of Zn, Sn, and Te with iodine ion assistant in teta and dien. The tetrahedral [SnTe4]4− anion coordinates to two [Zn(teta)]2+ units as a bidentate μ-1κ:2κ-SnTe4 ligand to form the neutral complex 1. It coordinates to three [Zn(teta)]2+ units with a tridentate μ3-1κ:2κ:3κ coordination modes, generating a complex cation [{Zn(teta)}3(μ3-1κ:2κ:3κ- SnTe4)]2+ in 2. In 3, the [Sn2Te6]4− anion joins two [Zn(tren)]2+cations with the trans terminal Te atoms, forming neutral complex 3. The μ-1κ:2κ-SnTe4, μ3-1κ:2κ:3κ-SnTe4, and μ-1κ:2κ-Sn2Te6 ligands to TM centers in 1–3 have not been observed before. Compound 4 contains a normal [Sn2Te6]4− and an abnormal [(Sn2Te6)0.75(Sn2Te8)0.25]4− anions. Compounds 1–4 exhibit narrow band gaps in the range of 1.47–1.98 eV, and a distinct red-shift of the band gaps is observed from 4 to 1−3.

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, 4 and 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]n(2n-) anion. It is connected with [Pb(tepa)](2+)via iodine atoms to form a 3-D network of [(tepa)(PbAg2I4)]n. In 6, the CO3(2-) 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)]n(n+)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.

Solvothermal reactions of Ln2O3, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien)2(μ-1κ,2κ2-AsS4)]n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien)2(1κ2-AsS4)] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln2O3 oxides were converted to [Ln(dien)2]3+ complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS4 unit. In 1−3, the AsS4 units interconnect the [Ln(dien)2]3+ cations via Ln−S bonds as tridentate μ-1κ,2κ2-AsS4 bridging ligands, resulting in the neutral coordination polymers [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln1). In 4−6, the AsS4 units coordinate with the Ln3+ ion of [Ln(dien)2]3+ as 1κ2-AsS4 chelating ligands to form neutral coordination compounds [Ln(dien)2(1κ2-AsS4)] (Ln2). The Ln3+ ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln3+ ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV.

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 cluster, 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 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 ...

Lanthanide selenidostannates (H3O)n[Ce(tepa)(μ-1κ2:2κ2-Sn2Se6)]n (1), [{Yb(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)]n·nH2O (2), [Htrien]2[{Ln(trien)(tren)}2(μ-1κ:2κ-Sn2Se6)][Sn2Se6] (Ln=Ce(3), Nd(4)) and [{Yb(dien)2}2(μ-OH)2]Sn2Se6 (5) were solvothermally prepared in different ethylene polyamines. The Sn2Se6 unit connects [Ce(tepa)]3+ and [{Yb(tepa)(μ-OH)}2]4+ fragments with tetradentate μ-1κ2Se1,Se2:2κ2Se5,Se6 and bidentate μ-1κSe1:2κSe5 bridging coordination modes in tepa, to form polymers 1 and 2, respectively. It joins two [Ln(trien)(tren)]3+ fragments as a μ-1κSe1:2κSe5 ligand to form binuclear complexes 3 and 4 in trien. Unlike the Sn2Se6 units in 1–4 that bind with Ln(III) centers as Se-donor ligands, the Sn2Se6 unit in 5 exists as a discrete ion. The syntheses of 1–5 show that the ethylene polyamines play an important role in the complexation of Sn2Se6 ligand with Ln(III) centers. Compounds 1–5 exhibit optical band gaps in the range of 2.09–2.42 eV, which are influenced by the complexation of Sn2Se6 with Ln(III) centers.

Organic hybrid europium hexachalcogenidodistannates [{Eu(en)3}2(μ-OH)2]Sn2S6 (1), [{Eu(en)3}2(μ-OH)2]Sn2Se6 (2), and [Eu(dien)3]2[(Sn2S6)(SH)2] (3) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally synthesized by the reactions of Sn, S (or Se) and Eu2O3 in en and dien solvents, respectively. Compounds 1–3 crystallize in monoclinic space group P21/n. Crystallographic data for 1: a = 10.1158(13), b = 11.3793(14), c = 14.9487(15) A, β = 98.209(4)°, V = 1703.1(3) A3, Z = 2. For 2: a = 10.1359(19), b = 11.771(2), c = 15.423(3) A, β = 99.322(5)°, V = 1815.8(6) A3, Z = 2. For 3: a = 11.6559(10), b = 15.1677(13), c = 14.1732(13) A, β = 95.682(2)°, V = 2493.4(4) A3, Z = 2. The Eu3+ ion forms binuclear tetravalent [{Eu(en)3}2(μ-OH)2]4+ complex cation to act as counter ion to the [Sn2S6]4− and [Sn2Se6]4− anions in 1 and 2. But it is coordinated with three dien ligands to form the mononuclear trivalent [Eu(dien)3]3+ complex cation in 3. The cations and anions are connected into 3-dimensional networks via O–H···S, N–H···S, or N–H···Se hydrogen bonds, respectively. New europium hexachalcogenidodistannate [{Eu(en)3}2(μ-OH)2]Sn2S6, [{Eu(en)3}2(μ-OH)2]Sn2Se6, and [Eu(dien)3]2[(Sn2S6)(SH)2] with 3-dimensional H-bonding network structures were respectively prepared in ethylenetediamine (en) and diethylenetetriamine (dien) under mild solvothermal conditions.

Two types of 4f–3d thiostannates with general formula [Hen]2[Ln(en)4(CuSn3S9)]⋅0.5 en (Ln1; Ln=La, 1; Ce, 2) and [Hen]4[Ln(en)4]2[Cu6Sn6S20]⋅3 en (Ln2; Ln=Nd, 3; Gd, 4; Er, 5) were prepared by reactions of Ln2O3, Cu, Sn, and S in ethylenediamine (en) under solvothermal conditions between 160 and 190 °C. However, reactions performed in the range from 120 to 140 °C resulted in crystallization of [Sn2S6]4− compounds and CuS powder. In 1 and 2, three SnS4 tetrahedra and one CuS3 triangle are joined by sharing sulfur atoms to form a novel [CuSn3S9]5− cluster that coordinates to the Ln3+ ion of [Ln(en)4]3+ (Ln=La, Ce) as a monodentate ligand. The [CuSn3S9]5− unit is the first thio-based heterometallic adamantane-like cluster coordinating to a lanthanide center. In 3–5, six SnS4 tetrahedra and six CuS3 triangles are connected by sharing common sulfur atoms to form the ternary [Cu6Sn6S20]10− cluster, in which a Cu6 core is enclosed by two Sn3S10 fragments. The topological structure of the novel Cu6 core can be regarded as two Cu4 tetrahedra joined by a common edge. The Ln3+ ions in Ln1 and Ln2 are in nine- and eightfold coordination, respectively, which leads to the formation of the [CuSn3S9]5− and [Cu6Sn6S20]10− clusters under identical synthetic conditions. The syntheses of Ln1 and Ln2 show the influence of the lanthanide contraction on the quaternary Ln/Cu/Sn/S system in ethylenediamine. Compounds 1–5 exhibit bandgaps in the range of 2.09–2.48 eV depending on the two different types of clusters in the compounds. Compounds 1, 3, and 4 lost their organic components in the temperature range of 110–350 °C by multistep processes.

New heterometallic thioantimonates(III) [Co(dien)2]HgSb2S5 (1), [Ni(dien)2]HgSb2S5 (2) and [H2dien]HgSb8S14 (3), and a mixed-valent thioantimonate(III,V) [Co(dien)2]2Sb4S9 (4) were solvothermally prepared in diethylenetriamine (dien) solvent from Co(Ni)–Hg–Sb–S, Hg–Sb–S and Co–Sb–S systems, respectively. In 1 and 2, the bimeric subunit Sb2S5 condenses with HgS4 tetrahedron via sharing common S atoms to form an one-dimensional [HgSb2S5]n2n− chain, in which a new μ3-1κ2S1,S5:2κS2:3κS4 bridging mode of the Sb2S5 subunit is obtained. In 3, four SbS3 trigonal pyramids and a linear HgS2 unit condense via sharing S atoms to generate an one-dimensional double-lined [HgSb8S14] n2n− chain. In 4, three SbIIIS3 pyramids and a SbVS4 tetrahedron share common corners to form an one-dimensional mixed-valent [Sb4S9]n4n− anion. The syntheses of 1–4 demonstrated that the Hg2+ ion is easily incorporated into thioantimonate networks, and has a higher affinity to S than that of transition metals. 1–4 exhibit semiconducting properties with optical band gaps in 2.0–2.4 eV.