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We demonstrate that [Co(2,2′-bipy)3]Ag3I6 with a hole structure facilitates dye adsorption and photocatalytic reduction.

We synthesized a new iodoargentate [Co(2,2'-bipy)

Sensitive monitoring of intracellular uracil-DNA glycosylase (UDG) in living cells is essential to understanding the DNA repair pathways and discovery of anticancer drugs. Herein, we demonstrate the construction of an entropy-driven dumbbell-type DNAzyme assembly circuit for lighting up UDG in living cells via the integration of entropy-driven DNA catalysis (EDC) with the DNAzyme biocatalyst. Target UDG excises the damaged uracil base, causing the breakage of detection probe and the release of trigger. The released trigger can initiate the downstream EDC reaction to form two catalytically active DNAzyme units. The resultant dual Mg

We synthesized and characterized three types of isostructural iodoargentates, [TM(phen)3]Ag2I4·3DMF (TM = Co (1), Ni (2), Zn (3)), [TM(phen)3]Ag3I5·DMF (TM = Co (4), Ni (5), Zn (6)), and [TM(phen)3...

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.

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.

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.

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.

[Fe(phen)3]Sb6Se10 is prepared by solvothermal reaction of a 1:2:6 molar mixture of Fe, Sb, Se with phen and DABCO in MeOH/H2O (3:1) mixed solvent (autoclave, 150 °C, 6 d).

The new hybrid silver thiostannates (enH)4[Ln(en)4]2 [Ag6Sn6S20]·3en (Ln: Er, Tm, Yb) are solvothermally prepared from mixtures of Ln2O3, Ag, Sn, and S in en (180 °C, 6 d).

Compounds (IV), (V), and (VII) are solvothermally prepared and characterized by single crystal XRD and UV/VIS spectroscopy.

Polysulfido-thioantimonate [Co(phen)3][Sb4S5(S4)2] (1) and thioantimonates [Co(phen)3]2Sb18S29 (2) and [H3O][Co(phen)3]SbS4·9H2O (3) (phen = 1,10-phenanthroline) were prepared using [Co(phen)3]2+ formed in situ as a structure directing agent in 80% and 50% CH3OH aqueous solution or water solution, respectively. In 1, eight Sb3+ ions are connected by ten μ-S2– and four μ-S42– 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 ψ-SbS4 geometries. In 2, sixteen SbS3 and two ψ-SbS4 units are interconnected by sharing S atoms to form a three-dimensional [Sb18S294–]∞ framework containing an interpenetrating channel system, in which the [Co(phen)3]2+ complexes are enclosed. In 3, by O-H···O and O-H···S H-bonding, [SbS4]3–, H2O and H3O+ are interconnected into a {H3O-SbS4-(H2O)9}n2n– anionic layer, which contains a (H2O)6 water cluster. The [Co(phen)3]2+ complexes are located between the layers. The syntheses of 1-3 show the influences of different solvents on the Co/Sb/S/phen system. The optical band gaps of 1-3 are 2.02, 2.11, and 2.27 eV, respectively.

The new selenidostannates (IV) and (V) are hydrothermally synthesized in the presence or absence of KSCN, respectively.

The Cr-containing selenidostannates (IV) and (V) are ionothermally synthesized and characterized by single crystal XRD and solid state optical diffuse reflectance spectroscopy.

In aqueous solution, Co2+ and Ni2+ ions can be coordinated not only by polyamines but also by As2S3 or AsS3 units as in (III) and (IV).

Solvothermal reactions of Ln2O3, As and S in diethylenetriamine (dien) (autoclave, 170 °C, 6 d) yields two structural types of lanthanide thioarsenates of general formulae [Ln(dien)2(μ-1ϰ,2ϰ2-AsS4)] n (Ln: Sm, Eu, Gd) and [Ln(dien)2(1ϰ2-AsS4)] (Ln: Tb, Dy, Ho) in 45—57% yield.

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 Co(3+) 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 η(1)-As1,η(2)-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 [As2S5](4-), respectively. The band gaps of 1-3 are in the range of 1.37-1.55 eV, and the 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.

Compounds (IV), (VI), and (VIII) are characterized by XRD and UV/VIS reflectance spectroscopy.

The new compounds (V), (VII), and (IX) crystallize in the monoclinic space group P21/c with Z = 4, and (VIII) in the monoclinic space group P21/n with Z = 2 (single crystal XRD).

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 Ln(3+) 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.

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]n3n−via face-sharing. The [Ag2Pb2I9]n3n− 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]n3n− chain, which represents a new member of iodoplumbate aggregates. In the [(DMSO)Pb4I11]n3n− 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.

Heterometallic Pb-Ag iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(1), Pr(2)] were prepared by the reactions of PbI2, AgNO3 and KI in dimethylformamide (DMF) templated by [Ln(DMF)8](3+) complexes formed in situ by stirring LnCl3 in DMF. The same reactions in the absence of AgNO3 or PbI2 afforded iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31 (3), and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(4), Pr(5)], respectively. Compounds 1 and 2 contain a ternary one-dimensional polymeric [Pb3Ag10I22](6-) anion self-assembled from five AgI4, one PbI6 and one PbI4 primary units via edge- and face-sharing. Twelve PbI6 octahedra are interlinked via sharing of common faces to generate a 1D zigzag [Pb11I31(9-)]n chain in 3, which represents a new member of iodoplumbate aggregates. In 4 and 5, three AgI4 tetrahedra connect through common edges to form the [Ag6I12](6-) building block. The [Ag6I12](6-) blocks are further interlinked by sharing common edges, resulting in the 1D [Ag6I9(3-)]n chain. Optical absorption spectra showed that the synthesized Ag-iodoplumbate and iodoplumbate have potential for being used as semiconductors. Our results show that heterometallic halometallate properties can be tuned by combining structural units with different symmetries, enabling the synthesis of specific functional materials.