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May 11, 2017 - optical materials,1 conductors or semiconductors,2 photo- or electrocatalysis,3 ion .... grade and were used as received. N2H4 is 98% a...
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Hydrazine-Assisted Syntheses and Properties of Mercury Tellurides Containing Transition-Metal Complexes Peipei Sun, Shuzhen Liu, Shufen Li, Limei Zhang, Hui Sun, and Dingxian Jia* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China S Supporting Information *

ABSTRACT: 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-(2aminoethyl)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 and E are the first examples of telluromercurates incorporated with TM complex units via TM−Te bonds. Compound F contains fivefold coordinated [Zn(atep)]2+ cations and zigzag [Hg5Te124−]n polymeric anion. The [Hg5Te124−]n 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 A−F 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 C.

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INTRODUCTION The chemistry of transition-metal (TM) chalcogenides has received considerable attention due to their diverse structures and various potential applications in the area of magnetic and optical materials,1 conductors or semiconductors,2 photo- or electrocatalysis,3 ion exchange,4 energy storage,5 and hydrogen evolution.6 Over the past few decades, a tremendous amount of research has been conducted on TM chalcogenides, and many sulfido- or selenometalates have been prepared with different synthetic techniques and structurally characterized.7 Unlike sulfur and selenium, which usually afforded metal sulfides and metal selenides in solutions, the heavier tellurium preferred formation of polytellurides with metals in the syntheses from solutions.8 It had been found that primary amines (such as ethylenediamine (en)) and other polar organic solvents (such as dimethylformamide (DMF)) were particularly suitable solvents for syntheses of metal tellurides. Solvent extraction of binary or ternary intermetallic telluride precursors in liquid ammonia or organic amine solutions has produced a number of TM polytelluride anions [Ni4Te20]4−,9 [Mo4Te16(en)4]2−,10 [M2Te12]4− (M = Cu, Ag),11 [MTe7]3− (M = Ag, Au),12,13 [Au9Te7]4−,14 [Au4Te4(en)4]2−,14 [MTe7]2− (M = Zn, Hg),12,15 [MTe8]2− (M = Zn, Cd, Hg, Pd),16 [HgTe2]2−,17 [Hg2Te4]2−,8 [Hg2Te5]2−,18 and [M4Te12]4− (M = Cd, Hg).18,19 Electrochemical syntheses using metal telluride alloy as electrodes in © XXXX American Chemical Society

nonaqueous solvents had afforded polytellurometalates containing [HgTe7(en)0.5]2− 8 and [Au3Te4]3−.20 In addition, reactions in molten polytelluride salts (flux method) had generated copper tellurides [Cu8Te10]3− and [Cu8Te11]4−.21 Currently, solvothermal synthesis in amine solution has proven to be a powerful approach to the preparation of thiometalates and selenometalates of main-group metals.22 Comparatively, the solvothermal synthesis of tellurometalates, especially the tellurometalates of transition metals, had been less explored. Currently, in the TM−Hg−Te ternary system, few organic hybrid telluromercurates, namely, [{Mn(en)3}2Cl2]Hg2Te4 and [TM(en)3]Hg2Te9 (TM = Fe, Mn), have been solvothermally synthesized.22b,23 It is noteworthy that ternary telluride alloy, such as mercury cadmium telluride (HgCdTe) and cadmium zinc telluride (CdZnTe), has also drawn high attention in semiconductors and infrared detectors recently.24 In recent years, the works of several groups have demonstrated that hydrazine (N2H4) is an excellent solvent or template for preparing metal chalcogenides, and a number of hydrazine adducts or complexes based on 15/16 and 14/16 chalcogenidometalates had been prepared in hydrazine at room temperature or under solvothermal conditions.25,26 Mitzi Received: January 18, 2017

A

DOI: 10.1021/acs.inorgchem.7b00115 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

1315 (m), 1173 (w), 1135 (w), 1080 (s), 1004 (s), 946 (s), 883 (s), 816 (s), 706 (w), 592 (s), 483 (s), 429 (m), 410 (w). Synthesis of [Zn(trien)(N2H4)2]Hg2Te4 (B). Black block crystals of B were prepared and collected with a procedure similar to that for the synthesis of A, except that ZnCl2 was used instead of MnCl2·4H2O. Yield: 0.121 g (51% based on HgCl 2 ). Anal. Calcd for C6H26N8ZnHg2Te4 (1187.30): C, 6.07; H, 2.21; N, 9.44. Found: C, 5.94; H, 2.12; N, 9.31%. IR (KBr, cm−1): 3460 (s), 3270 (m), 3106 (w), 2922 (w), 2064 (m), 1656 (s), 1589 (s), 1526 (w), 1463 (m), 1379 (s), 1274 (w), 1118 (s), 1072 (w), 996 (s), 950 (s), 861 (w), 786 (m), 673 (w), 618 (s), 542 (m), 479 (s), 424 (m), 408 (w). Synthesis of [Mn(tepa)(N2H4)]2Hg4Te12 (C). Compound C was prepared with a procedure similar to that for the synthesis of 1, except that tepa was used instead of trien. Dark black cube crystals of C were separated from a small amount of black powder with tepa/C2H5OH mixture using the methods described in the synthesis of A. Yield: 0.156 g (54% based on HgCl2). Anal. Calcd for C16H54N14Mn2Hg4Te12 (2886.17): C, 6.66; H, 1.89; N, 6.79. Found: C, 6.48; H, 1.82; N, 6.61%. IR (KBr, cm−1): 3335 (m), 3258 (s), 3172 (m), 2941 (w), 1627 (s), 1588 (s), 1481 (s), 1383 (s), 1190 (s), 1113(s), 1065 (s), 989 (m), 804 (w), 767 (w), 659 (m), 591 (s), 535 (w), 417 (w). Synthesis of [Mn(trien){Hg2Te4}] (D). MnCl2·4H2O (40 mg, 0.20 mmol), HgCl2 (109 mg, 0.40 mmol), Te (153 mg, 1.20 mmol), and N2H4 (159 mg, 4.95 mmol) were dispersed in 3 mL of trien by stirring, and the dispersion was loaded into a PTFE-lined stainless steel autoclave of volume 10 mL. The sealed autoclave was heated to 120 °C for 6 d and then cooled to ambient temperature. The resulting products contained black crystals of D and small amount of black powder. Crystals were separated from black powder using the methods described in the synthesis of A. Yield: 0.151 g (68% based on HgCl2). Anal. Calcd for C6H18N4MnHg2Te4 (1112.76): C, 6.48; H, 1.63; N, 5.03. Found: C, 6.32; H, 1.58; N, 4.93%. IR (KBr, cm−1): 3431 (s), 3044 (m), 2963 (m), 2779 (s), 2446 (m), 2085 (m), 1732 (s), 1631 (s), 1471 (s), 1412 (m), 1353 (w), 1320 (m), 1202 (w), 1173 (m), 1101 (w), 1022 (s), 887 (w), 820 (w), 765 (m), 681 (s), 597 (w), 471 (m), 415 (w). Synthesis of [Zn(trien){Hg2Te4}] (E). ZnCl2 (27 mg, 0.20 mmol), HgCl2 (109 mg, 0.40 mmol), Te (153 mg, 1.20 mmol), and N2H4 (162 mg, 5.06 mmol) were dispersed in 3 mL of trien by stirring, and the dispersion was loaded into a PTFE-lined stainless steel autoclave of volume 10 mL. The sealed autoclave was heated to 130 °C for 6 days and then cooled to ambient temperature. Black block crystals of E were collected with a procedure similar to that for the synthesis of A. Yield: 0.141 g (63% based on HgCl 2 ). Anal. Calcd for C6H18N4ZnHg2Te4 (1123.19): C, 6.42; H, 1.62; N, 4.99. Found: C, 6.35; H, 1.48; N, 4.81%. IR (KBr, cm−1): 3472 (s), 3010 (s), 2766 (m), 2648 (w), 1626 (s), 1458 (s), 1412 (m), 1379 (s), 1202 (w), 1160 (m), 1105 (w), 1017 (s), 879 (w), 802 (m), 655 (w), 559 (w), 479 (m), 407 (w). Synthesis of [Zn(atep)]2Hg5Te12 (F). ZnCl2 (27 mg, 0.20 mmol), HgCl2 (109 mg, 0.40 mmol), Te (153 mg, 1.20 mmol), and N2H4 (235 mg, 7.32 mmol) were dispersed in 3 mL of tepa by stirring, and the dispersion was loaded into a PTFE-lined stainless steel autoclave of volume 10 mL. The sealed autoclave was heated to 120 °C for 6 d and then cooled to ambient temperature. The resulting products contained black crystals of F and small amount of black powder. Crystals were separated and collected using the methods described in the synthesis of A. Yield: 0.134 g (55% based on HgCl2). Anal. Calcd for C16H46N10Zn2Hg5Te12 (3043.52): C, 6.31; H, 1.52; N, 4.60. Found: C, 6.18; H, 1.43; N, 4.53%. IR (KBr, cm−1): 3236 (s), 3133 (m), 2945 (w), 2877 (w), 1644 (s), 1601 (s), 1485 (w), 1422 (m), 1387 (s), 1288 (w), 1246 (m), 1134 (s), 1079 (s), 1023 (s), 950 (s), 835 (w), 689 (w), 664 (m), 536 (w), 449 (w), 413 (w). X-ray Crystal Structure Determination. All data were collected on a Rigaku Saturn CCD diffractometer at 293(2) K using graphitemonochromated Mo Kα radiation (λ = 0.710 73 Å) with an ω-scan method to a maximum 2θ value of 50.70°. An absorption correction was applied for all the compounds using multiscan. The structures were solved with direct methods using the program of SHELXS-9729a and refined by a full matrix least-squares technique based on F2 using

prepared a hydrazine adduct of zinc telluride by the reaction of ZnTe and Te at room temperature.27 It is well-known that hydrazine is a basic solvent with high polarity, as well as a strong ligand with less steric hindrance. As a result, hydrazine could dissolve the metal chalcogenide species and was helpful in the growth of crystalline chalcogenides. So the use of hydrazine enables improvement in the solvothermal reactions and promotes the formation of novel chalcogenide materials with different structural dimensionalities.25c,26a,f Furthermore, hydrazine possesses strong reduction ability. It would readily reduce chalcogens to chalcogenide anions to form chalcogenidometalates with metal ions when chalcogens were used as the starting materials in the synthesis. Now, the ternary TM/Hg/ Te (TM = Mn, Zn) system was investigated in ethylene polyamines with the coexistence of N2H4 for the first time. Ternary telluromercurates [Mn(trien)(N2H4)2]2[Hg2Te4]2 (A), [Zn(trien)(N2H4)2]Hg2Te4 (trien = triethylenetetramine) (B), [Mn(tepa)(N2H4)]2Hg4Te12 (tepa = tetraethylenepentamine) (C), [TM(trien)(Hg2Te4)] (TM = Mn (D), Zn(E)), and [Zn(atep)] 2 Hg 5 Te 12 (atep = 4-(2-aminoethyl)triethylenetetramine) (F) were prepared using tellurium powder as the sole Te source with the assistance of reactive hydrazine molecule under solvothermal conditions. As far as we know, D and E are the first examples of telluromercurates incorporated with a TM complex unit. Herein, we report the solvothermal syntheses, crystal structures, and photocatalytic and thermal properties of compounds A−F.

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EXPERIMENTAL SECTION

Materials and Methods. All starting chemicals except N2H4 are of analytical grade and were used as received. N2H4 is 98% aqueous solution. Elemental analyses were conducted using an EA1110-CHNSO elemental analyzer. Fourier transform infrared (FT-IR) spectra were recorded on a Nicolet Magna-IR 550 spectrometer using dry KBr discs over the 4000−400 cm−1 range. Optical diffuse reflectance spectra of powder samples were obtained at room temperature using a Shimadzu UV-3150 spectrometer. Absorption (α/S) data were calculated from the reflectance using the Kubelka−Munk function α/S = (1 − R)2/ 2R.28 Thermogravimetric analyses (TGA) were conducted on an TG 6300 microanalyzer. The samples were heated at a rate of 5 °C min−1 under a nitrogen stream of 100 mL min−1. Powder X-ray diffraction (XRD) patterns were collected on a D/MAX-3C diffractometer using graphite monochromatized Cu Kα radiation (λ = 1.5406 Å). The photocatalytic activities of the samples were evaluated by the degradation of crystal violet (CV) under visible-light irradiation of a 380 W Hg lamp. The resulting solution was analyzed on a PE Lambda 35 UV/vis spectrophotometer. Synthesis of [Mn(trien)(N2H4)2]2[Hg2Te4]2 (A). MnCl2·4H2O (40 mg, 0.20 mmol), HgCl2 (109 mg, 0.40 mmol), Te (153 mg, 1.20 mmol), and N2H4 (1027 mg, 31.4 mmol) were dispersed in 2 mL of trien by stirring. The resulting dispersion was loaded into a polytetrafluoroethylene (PTFE)-lined stainless steel autoclave of volume 10 mL. Caution! Hydrazine is highly toxic and explosive, and it should be handled caref ully. The sealed autoclave was heated to 120 °C for 6 d and then cooled to ambient temperature. The resulting products contained gray black crystals of A and some black powder. The crude product was transferred into a vial, which was filled with trien/C2H5OH (1:1 (v/v)). Most of the black powder was suspended in the solution, which was decanted leaving crystals behind. This procedure was repeated until the solution remained clear. The black crystals were collected by filtration, washed with ethanol, and stored under a vacuum. Yield: 0.134 g (57% based on HgCl2). Anal. Calcd for C12H52N16Mn2Hg4Te8 (2353.74): C, 6.12; H, 2.23; N, 9.52. Found: C, 5.93; H, 2.15; N, 9.38%. IR (KBr, cm−1): 3455 (s), 3250 (m), 2943 (m), 2867 (m), 1719 (w), 1635 (w), 1564 (w), 1458 (m), 1383 (m), B

DOI: 10.1021/acs.inorgchem.7b00115 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 1. Crystal Data and Summary of X-ray Data Collection A

B

C

empirical formula fw cryst syst space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å3 Z T, K calcd density, g cm−3 F(000) 2θ (max), deg total reflns collected unique reflns Rint no. of param R1 [I > 2σ(I)] wR2 (all data) Δρmax, e Å−3 Δρmin, e Å−3 GOF on F2

C12H52N16Mn2Hg4Te8 2353.74 monoclinic P21/c 16.745(3) 18.245(4) 14.769(3) 90 98.11(3) 90 4467.0(16) 4 293(2) 3.500 4088 50.70 42 780 8148 0.0851 418 0.0563 0.1097 1.780 −2.327 1.133 D

C6H26N8ZnHg2Te4 1187.30 orthorhombic Pbca 14.875(3) 16.460(3) 18.027(4) 90 90 90 4413.7(15) 8 293(2) 3.574 7632 50.70 24 328 4027 0.0630 187 0.0479 0.0975 1.646 −2.204 1.144 E

C16H54N14Mn2Hg4Te12 2886.17 triclinic P1̅ 9.9951(4) 10.8781(6) 13.5035(6) 100.359(4) 95.983(4) 112.611(4) 1308.74(11) 1 293(2) 3.662 1242 50.70 14 876 4770 0.0472 217 0.0447 0.0952 1.999 −2.219 0.991 F

empirical formula fw cryst syst space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å3 Z T, K calcd density, g cm−3 F(000) 2θ (max), deg total reflns collected unique reflns Rint no. of param R1 [I > 2σ(I)] wR2 (all data) Δρmax, e Å−3 Δρmin, e Å−3 GOF on F2

C6H18N4MnHg2Te4 1112.76 monoclinic P21/n 8.6036(17) 19.152(4) 11.367(2) 90 101.49(3) 90 1835.5(6) 4 293(2) 4.027 1900 50.70 17 500 3363 0.0718 155 0.0410 0.0973 2.151 −1.175 1.126

C6H18N4ZnHg2Te4 1123.19 monoclinic P21/c 8.5682(17) 18.9544) 12.915(4) 90 119.31(2) 90 1828.9(8) 4 293(2) 4.079 1920 50.70 8439 3321 0.0508 148 0.0409 0.0968 2.599 −1.459 1.024

C16H46N10Zn2Hg5Te12 3043.52 monoclinic C2/c 24.5615(8) 15.0586(5) 15.7660(4) 90 123.122(3) 90 4883.7(3) 4 293(2) 4.139 5184 50.70 13 886 4466 0.0577 204 0.0358 0.0778 1.800 −1.759 1.022

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SHELXL-97.29b All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were added geometrically and refined using the riding model. Atom C(6) in compound A is disordered with the occupancies being refined as 50% and 50%. The disordered atom C(6) compound B was refined as 60% and 40% occupancies. Hydrogen atoms were added geometrically and refined using the riding model. The hydrogen atoms of disordered C atoms were not dealt with. Technical details of data acquisition and selected refinement results are summarized in Table 1.

RESULTS AND DISCUSSION

Syntheses. Crystalline organic hybrid telluromercurate compounds have been known for a long time. These telluromercurates are usually prepared using binary alkali tellurides or ternary telluromercurate salts, such as Li2Te, Rb2Te, and K2Hg2Te3 as tellurium precursors.8,12,18 The precursors were usually prepared under harsh experimental conditions. In this work, novel TM-telluromercurates were C

DOI: 10.1021/acs.inorgchem.7b00115 Inorg. Chem. XXXX, XXX, XXX−XXX

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molecules.25a,c The purity of bulk phases of title compounds were investigated using PXRD. The PXRD patterns of the bulk phases of title compounds are consistent with the simulated PXRD patterns based on single-crystal XRD data (Figures S7− S12), respectively. Crystal Structures of A and B. Compound A crystallizes in the monoclinic space group P21/c (No. 14), while B crystallizes in the orthorhombic space group Pbca (No. 61). However, they have similar molecular compositions and structures. Compound A consists of two crystallographically independent [Mn(trien)(N2H4)2]2+ complex cations and two one-dimensional (1D) [Hg2Te42−]n polyanions. The Mn(1)2+ and Mn(2)2+ ions are both coordinated by four N atoms of a trien ligand and two N atoms of two N2H4 molecules, forming [Mn(trien)(N2H4)2]2+ complex cations (Figure 1). Mn(1)2+

synthesized using tellurium powder as the sole Te source with the assistance of hydrazine molecule under solvothermal conditions in the lower temperature range (Scheme 1). The Scheme 1. Solvothermal Synthesesa of Compounds A−F

a

The amount of N2H4 is 4−6 equiv to Te.

reactions MnCl2·4H2O (or ZnCl2), HgCl2, and Te in N2H4/ trien or N2H4/tepa mixed solvent at 120 °C for 6 d produced crystals of [Mn(trien)(N2H4)2]2[Hg2Te4]2 (A), [Zn(trien)(N2H4)2]Hg2Te4 (B), and [Mn(tepa)(N2H4)]2Hg4Te12 (C), respectively. Hydrazine and polyamine trien (tepa) molecules both take part in the coordination to the Mn(II) and Zn(II) centers. The reactions with decreasing amount of hydrazine (N2H4 was used in 4−6 equiv to Te) at the same temperature afforded [Mn(trien) (Hg2Te4)] (D), [Zn(trien) (Hg2Te4)] (E) and [Zn(atep)]2Hg5Te12 (F), respectively. The branched pentadentate amine 4-(2-aminoethyl)triethylenetetramine (atep) might come from the rearrangement of tepa during the solvothermal reaction. Similar isomerization of linear ethylene polyamines to give branched isomers had also been observed in the synthesis of thioantimonates and selenidostannates under solvothermal conditions.30 Although N2H4 was not bound in the final structures of compounds D−F, it plays an important role in the crystal growth. No D−F were obtained in the separate experiments conducted under the same condition without addition of N2H4. Furthermore, no crystalline telluromercurate compounds can be obtained by the reactions of MnCl2·4H2O (or ZnCl2), HgCl2, and Te in trien or tepa without N2H4 even at higher temperature range of 120−200 °C. It is worthy to note that an Fe(II) telluromercurate [Fe(en)3]Hg2Te9 was prepared by solvothermal methods in en at 160 °C using both Rb2Te and Te as starting materials.23 N2H4 might play an important role in converting elemental Te to telluride anion when sole Te was used as the starting material in the syntheses. Being a strong reducing agent [as shown by the standard reducing potential: φθ (N2/N2H4) = −1.16 V]31 with high chemical reactivity, N2H4 can smoothly reduce elemental Te to telluride anion Te2− or polytelluride Te22− anion under solvothermal conditions by equations below:

Figure 1. Crystal structures of [Mn(1) (trien)(N2H4)2]2+ (a) and [Mn(2) (trien)(N2H4)2]2+ (b) complex cations with labeling scheme in compound A. Hydrogen atoms are omitted for clarity.

and Mn(2)2+ ions are both in distorted octahedral environments, as shown by N−Mn−N angles in the range of 151.5(10)−172.0(10)° (Table S1). The Mn−N bond lengths (2.22(2)−2.33(3) Å, Table S1) are in the range of those observed in other Mn(II) complexes containing N2H4 and trien ligands.25c,26a,32 There are four crystallographically independent Hg and eight Te atoms in the structure of compound A (Table S1). The Hg(1)2+ and Hg(2)2+ ions are joined by a Te2− (Te(3)) and a Te22− (containing Te(2) and Te(4)) anions to form a five-membered heteroring Hg2Te3 with the Hg atoms at the 1 and 3 positions (Figure 2). The anion Te(1)2− binds with the Hg2Te3 ring at Hg(1) to complete the asymmetric Hg2Te4 unit of the structure. The asymmetric Hg2Te4 units are interconnected by sharing Te(1) atom yielding the 1D anion

N2H4 + 2Te + 4OH− = N2 + 2Te 2 − + 4H 2O N2H4 + 4Te + 4OH− = N2 + 2Te2 2 − + 4H 2O

Then, the Te2− and/or Te22− anions assemble with Hg(II) cation to form telluromercurate unit [HgxTey ]z−, and telluromercurate compound is formed. In the FT-IR spectra of A−F (Figures S1−S6), the absorptions located in the frequency range of 3460−3113 cm−1 could be assigned to the asymmetric and symmetric N−H stretching vibrations of the amino groups. The absorptions at ∼2940 and 2850 cm−1 are due to the C−H stretching vibrations. The bands located between 946 and 987 cm−1 in compounds A−C are attributed to the N−N vibrations of N2H4

Figure 2. Crystal structure of the polymeric anions [Hg2Te42−]n with labeling scheme in compound A, showing the Te···Te interactions between the polyanions. D

DOI: 10.1021/acs.inorgchem.7b00115 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry [Hg2Te42−]n (Figure 2), which is labeled as Hg2Te4(a). Another 1D anion [Hg2Te42−]n (Figure S13), which is labeled as Hg2Te4(b), is constructed by two Hg (Hg(3), Hg(4)) and four Te (Te(5)−Te(8)) atoms with the same connections as the Hg2Te4(a) chain. Between the Hg2Te4(a) chains, Te···Te interaction is observed between Te(1) and Te(4) with Te···Te distance of 3.797 Å, which is shorter than the sum of the van der Waals radii of two Te atoms (4.18 Å).33 With the Te···Te interaction, the Hg2Te4(a) chains are connected into an anionic layer (marked as [Hg2Te4(a)]n) perpendicular to the a axis of the unit cell (Figure 2). The Hg2Te4(b) chains also form an anionic layer (marked as [Hg2Te4(b)]n) via the Te···Te interaction between Te(5) and Te(6) (Te···Te = 3.759 Å; Figure S13). The [Hg2Te4(a)]n and [Hg2Te4(b)]n layers run parallel and are separated by [Mn(trien)(N2H4)2]2+ complex cations alternatively (Figure 3). In compound A, there are short

N−H···Te hydrogen bonds with H···Te distances in the range of 2.75−3.30 Å (Table S7). In the compounds A and B, the Hg−Te, and Te−Te lengths range from 2.673(2) to 2.7923(15) Å, and from 2.7698(17) to 2.788(3) Å (Tables S1 and S2), respectively. They are similar to the corresponding bond lengths observed in the telluromercurate (Et 4 N) 2 [Hg 2 Te 4 ] (Hg−Te: 2.683(5)− 2.791(5) Å, Te−Te: 2.767(7) Å), (Me4N)4[Hg3Te7]·0.5en (Hg−Te: 2.691(2)−2.792(2) Å, Te−Te: 2.729(3) and 2.734(3) Å),8 and [Fe(en)3]2Hg2Te9 (Hg−Te: 2.694 and 2.755 Å, Te−Te: 2.734 and 2.769 Å).23 All the Hg atoms have approximately trigonal-planar coordination with Te−Hg−Te angles between 114.22(7)° and 129.34(7)° (Tables S1 and S2). It is worth noting that the [Hg2Te42−]n anions in compounds A and B have different conformation from the anion of (Et4N)2[Hg2Te4], although these anions have the same compositions and structural connections. All the fivemembered Hg2Te3 heterorings in the [Hg2Te42−]n polyanions of compounds A and B are approximately coplanar (Figures 2, 3, S14, and S17). But the Hg2Te3 rings in the analogous anion [Hg2Te42−]n in (Et4N)2[Hg2Te4] are not coplanar.8 The difference might attributed to the weak intermolecular interactions found in A and B. In A and B, numerous N− H···Te interactions are formed on both sides of the Hg2Te3 rings (Figures, 3, S14, S17). In addition, Te···Te interactions are formed between the 1D [Hg2Te42−]n anions (Figures 2, S13, and S16). Crystal Structure of C. Compound C crystallizes in the triclinic crystal system with one formula unit in the unit cell. It consists of two [Mn(tepa)(N2H4)]2+ cations and a [Hg4Te12]4− anionic cluster. A tepa and a N2H4 molecule coordinate to a Mn2+ ion, forming the distorted octahedral [Mn(tepa)(N2H4)]2+ complex cation (Figure 4a). The Mn−N bond

Figure 3. Packing diagram of compound A, viewed along the c axis, showing the N−H···Te hydrogen-bonding network. Hydrogen atoms of CH2 groups are omitted for clarity.

intermolecular N−H···Te contacts with H···Te distances in the range of 2.83−3.29 Å (Table S7), which are shorter than the sum of the van der Waals radii of H and Te (3.50 Å),33 indicating weak N−H···Te hydrogen-bonding interactions. The N−H···Te interactions connect [Hg2Te42−]n anions and [Mn(trien)(N2H4)2]2+ cations into a three-dimensional (3D) network (Figure 3). [Mn(1) (trien)(N2H4)2]2+ cations assemble along the [Hg2Te42−]n anions, and [Mn(2) (trien)(N2H4)2]2+ reside the other side of the [Hg2Te42−]n anions (Figure S14). Compound B consists of one crystallographically independent [Zn(trien)(N2H4)2]2+ cation and one 1D [Hg2Te4]2− polyanion. The Zn2+ ion is coordinated by one trien and two N2H4 molecules forming an octahedral complex cation [Zn(trien)(N2H4)2]2+ (Figure S15), with Zn−N bond lengths varying by 2.168(17)−2.229(17) Å (Table S2), which are consistent with those observed in Zn(II) complex [{Zn(trien)}2(SnTe4)].34 The 1D anion [Hg2Te42−]n possesses the same crystal structure as the anion in compound A (Figure S16). It also forms an anionic layer via Te···Te interaction between the 1D chainlike anions (Te···Te = 3.729 Å; Figure S16). The anionic layers run parallel along the a axis and are separated by [Zn(trien)(N2H4)2]2+ complex cations (Figure S17). They interact with the complex cations via intermolecular

Figure 4. (a) Crystal structure of the [Mn(tepa)(N2H4)]2+ cation with labeling scheme in compound C. Hydrogen atoms are omitted for clarity. (b) Crystal structure of the [Hg4Te12]4− anionic cluster with labeling scheme, showing the asymmetric Hg2Te6 unit in compound C.

lengths (2.240(14)−2.348(12) Å; Table S3) are comparable to those found in other Mn(II) complexes containing tepa or N2H4 ligands.25c,26a,35 Note that TM complexes with trien or tepa ligands are commonly reported,32,34,35 but the TM complex units with mixed ligands trien/N2H4 or tepa/N2H4 found in compounds A−C are not observed before. The [Hg4Te12]4− cluster is composed from two crystallographically independent Hg and six Te atoms (Table S3). Hg(1)2+ and Hg(2)2+ ions are joined by a Te2− and a μ-Te22− anion to form a five-membered heteroring Hg2Te3 with the Hg atoms at the 1 and 3 positions (Figure 4b). The Hg2Te3 cycle unit is coordinated by a Te32− [containing Te(2), Te(3), Te(4)] anion at Hg(1) atom to give the asymmetric Hg2Te6 unit of the E

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Inorganic Chemistry structure (Figure 4b). The remaining part of the structure is generated by the center of crystallographical inversion to complete Hg coordination number of 4. In short words, the [Hg4Te12]4− cluster, which can be best given the formula [Hg4(Te2) (Te2)2(Te3)2]4−, is constructed by four Hg2+, two Te2−, two Te22−, and two Te32− ions (Figure 4b). It contains four-membered Hg2Te2, five-membered Hg2Te3, and sixmembered Hg2Te4 rings. Note that five atoms of the Hg2Te3 ring are not coplanar. The Te(1) of Hg2Te3 ring is out of the plane defined by two Hg atoms and Te2 unit. Contrarily, all atoms of the Hg2Te3 ring in compounds A and B are in a common plane and form a planar pentagon. All Hg2+ ions in the [Hg4Te12]4− cluster are tetrahedrally coordinated with four Te atoms. The tellurium atoms adopt μ2-Te [Te(1), Te(2), Te(4)] and μ3-Te [Te(5), Te(6)] bridging coordination modes to join the Hg and/or Te atoms. Correspondingly, the Hg−μ2Te bonds [2.6856(10)−2.7897(10) Å] are shorter than the Hg−μ3-Te bonds [2.9339(9)−3.0415(9) Å]. The bond lengths and angles (Table S3) are consistent with those observed in compound [nBu4N]4Hg4Te12.18 Short Te···Te interactions between the [Hg4Te12]4− clusters are observed in compound C. Each [Hg4Te12]4− cluster contacts four neighbors via weak Te···Te interactions among Te(1), Te(3), and Te(4) atoms (Figure 5). The Te···Te

Figure 6. Crystal structure of compound D with labeling scheme, showing the double chain [Hg2Te42−]n constructed by two single [Hg2Te4]n chains.

[Hg2Te42−]n in D can be described as a double chain constructed by two single [Hg2Te4] chains with compositions of the polyanions in A and B. Two [Hg2Te4] single chains are joined via Hg−Te bonds between Te22− and Hg2+ ions to form the double chain [Hg2Te42−]n of compound D. The double chain [Hg2Te42−]n binds the [TM(trien)]2+ units via TM−Te bonds between Te(1) and TM(II) to form the compounds D and E (Figures 6 and S20). The Mn−Te and Zn−Te bond lengths of 2.727(2) and 2.611(7) Å (Tables S4 and S5) are comparable with those reported in literature.27,34,36 Both Mn2+ and Zn2+ ions form tetragonal pyramids involving four N atoms from a trien and one Te atom from [Hg2Te42−]n (Figure S21). Two crystallographically independent Hg atoms are both tetrahedrally coordinated by two Te2− and two Te22− units. As a result, the Te22− anion acts a tetradentate μ4-1κ2:2κ2-Te2 ligand to join four Hg atoms in the double chains [Hg2Te42−]n of D and E (Figures 6 and S20), which is different from the Te22− unit of bidentate μ-1κ1:2κ1-Te2 chelating mode observed in the single chains [Hg2Te42−]n of A and B (Figures 2 and S16). The μ4-1κ2:2κ2-Te2 species such as the Te(3)−Te(4) pair in D and E are also observed in polytelluride Cs3Cu8Te10.21b The bond lengths of HgTe4 tetrahedrons (average (av) Hg− Te: 2.841 Å for D; 2.837 Å for E) in D and E are distinctly longer than the bond lengths with respect to the HgTe3 triangular units in A and B (av Hg−Te: 2.726 Å for A; 2.728 Å for B). Compared with the structures of the anions in compounds A and B, some special features of the double chains [Hg2Te42−]n in compounds D and E should be highlighted here. The Hg atoms are tetrahedrally coordinated by four Te atoms, and the Te22− units connect four Hg atoms with a tetradentate μ-1κ2:2κ2-Te2 chelating and bridging mode. Furthermore, the telluromercurate anions coordinate to the Mn(II) and Zn(II) centers in D and E. To the best of our knowledge, the integration of telluromercurate anions with TM complex units via TM−Te bonds had been not observed before. In the D and E, the 1D [TM(trien) (Hg2Te4)]n chains are connected into 3D networks via N−H···Te (H···Te 2.83− 3.29 Å; N−H···Te: 132.6−177.5°) hydrogen bonding between the chains (Figure 7). Crystal Structure F. Compound F crystallizes in the monoclinic crystal system with four formula units in the unit cell. It consists of [Zn(atep)]2+ cation and [Hg5Te124−]n polymeric anion. The Zn2+ ion is coordinated by five N atoms of atep forming a trigonal bipyramid ZnN5 with the axial angle N(2)−Zn(1)−N(4) of 162.3(3)° (Table S6 and Figure S22). The Zn−N bond lengths (2.059(8)−2.249(9) Å, Table

Figure 5. A view of the anionic layer assembled by the [Hg4Te12]4− clusters via Te···Te interactions in compound C. The HgTe4 units are shown in purple tetrahedra.

distance is 3.530 Å for Te(1)···Te(4) and 3.898 Å for Te(3)··· Te(3). As a result, the [Hg4Te12]4− clusters are interconnected by the Te···Te van der Waals interactions into a twodimensional (2D) layer perpendicular to the b axis (Figure 5). The layers run parallel with the [Mn(tepa)(N2H4)]2+ cations locating between the layers (Figure S18). Hydrogen bonding is observed between the [Hg4Te12]4− clusters and [Mn(tepa)(N2H4)]2+ cations. Each [Hg4Te12]4− cluster contacts six [Mn(tepa)(N2H4)]2+ cations via N−H···Te interactions (H···Te: 2.80−3.25 Å; N−H···Te: 143.8−166.5°; Table S7 and Figure S19). Crystal Structures of D and E. Compounds D and E are isostructural and consist of neutral organic hybrid coordination polymers [TM(trien) (Hg2Te4)]n (TM = Mn, Zn). The coordination polymers are composed of novel 1D chains with the compositions [Hg2Te4] decorated by [TM(trien)]2+ units at Te atoms via TM−Te bonds (Figure 6). The TM2+ ions are coordinated by a tetradentate trien ligand to form [TM(trien)]2+ units. As illustrated in Figure 6, the 1D anionic chain F

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that the [Hg5Te124−]n polyanion contains a polytelluride Te42− anion. The telluromercurates are commonly constructed by telluride anion Te2− and polytelluride anions Te22− and Te32−. The polytelluride Te42− anion is only previously observed in [PPh4]2[Hg(Te4)2], which contains single Te42− anions.16b The [Hg5Te124−]n polyanion contains Te2−, Te22−, and Te42− three types telluride anions. In F, all Hg atoms are tetrahedrally coordinated by four Te atoms with average bond length of 2.860 Å, and bond angles in the range of 88.90(2)−125.31(3)° (Table S6), which are in agreement with those found in D and E. The Te22− anion adopts the same coordination mode of tetradentate μ-1κ2:2κ2 as in D and E. The Te(4)2− ion acts as a tridentate μ3-Te bridging ligand to join three Hg atoms, which has been never observed before in mercury tellurides. The [Zn(atep)]2+ cation is located at the gaps between the [Hg5Te124−]n zigzag chains, and contacts the [Hg5Te124−]n chain via N−H···Te (H···Te: 2.84−3.19 Å; N−H···Te: 127.5−166.8°; Figure 9). Each [Hg5 Te 12 4− ]n chain is surrounded by six arrays of [Zn(atep)]2+ cations (Figure S23).

Figure 7. (a) Packing diagram of compound D, viewed along the a axis, showing N−H···Te intermolecular hydrogen bonding. (b) A view of 1D [Mn(trien) (Hg2Te4)]n chain of compound D. The HgTe4 units are shown in purple tetrahedra.

S6) are consistent with the corresponding bonds observed in E. As shown in Figure 8, the complicated [Hg5Te124−]n polyanion

Figure 9. A view of the N−H···Te interactions (dashed line) between [Zn(atep)]2+ cations and [Hg5Te124−]n polyanion in compound F. Hydrogen atoms of CH2 groups are omitted for clarity. The HgTe4 units are shown in purple tetrahedra.

Several binary mercury tellurides have been prepared by the solvent extraction or electrolysis methods using binary or ternary metal−tellurium alloys as precursors. Corbett obtained the first Hg−Te anion in the compound [crypt.K]2HgTe2, which was prepared by the reaction of an alloy of composition KHgTe with 4,7,13,16,21,24-hexaoxa-l,l0-diazabicyclo[8.8.8]hexacosane (2,2,2-crypt) in ethylenediamine (en).17 After this, Haushalter prepared (Et4N)2Hg2Te4, (Ph4P)2Hg2Te5, and (nBu4N)4Hg4Te12, by extraction of K2Hg2Te3 alloy with en in different organic solvents, and a (Me4N)4Hg3Te7·0.5en by electrochemical method using Hg2Te3 electrode in en solution. 8 , 1 8 Ibers prepared mercury polytellurides [PPh4]2[HgTe7] and [PPh4]2[Hg(Te4)2] using Li2Te and Te as tellurium sources in DMF solution.12,16b Müller’s group isolated a similar mercury polytelluride [K(15-crown-5)]HgTe7 from en solution using K2Te, Te, and 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5) as reactants.15 Li synthesized Rb4Hg5Te13 and [TM(en)3]Hg2Te9 (TM = Mn, Fe) by solvothermal reactions in en solvent at 160 °C using both

Figure 8. Crystal structure of the zigzag [Hg5Te124−]n polyanion in compound F, with labeling scheme, showing the [Hg4Te6] and [HgTe6] subunits.

can be described as interconnectivity of [Hg4Te6] and [HgTe6] two subunits. Two Hg2+ ions are joined by a Te2− and a Te22− anion to form a five-membered heteroring Hg2Te3. Two Hg2Te3 rings are coupled via four Hg−Te bonds between Hg2+ and Te22−, generating the [Hg4Te6] subunit (Figure 8). The second subunit [HgTe6] is composed from a Hg2+, a Te42−, and two Te2− ions. The Te42− anion adopts a μ-1κ1:2κ4-Te2 chelating coordination mode. Two Te atoms of the [HgTe6] units bridge four Hg atoms of two [Hg4Te6] subunits with a μTe mode. As a result, [Hg4Te6] and [HgTe6] subunits are connected into the 1D zigzag [Hg5Te124−]n polyanion. The connectivity generates six-membered Hg3Te3 and eightmembered Hg4Te4 rings in the [Hg5Te124−]n polyanion. Note G

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Inorganic Chemistry Rb2Te and Te precursors.22b,23,37 Rb4Hg5Te13 and [TM(en)3]Hg2Te9 are only transition-metal tellurides prepared by hydrothermal (solvothermal) methods so far. Now mercury compounds A−F are conveniently prepared by solvothermal methods with the help of highly reactive N2H4 molecule. Te powder was used as the sole tellurium source in the syntheses. The polymeric [Hg2Te42−]n and [Hg5Te124−]n anions in D−F represent new species for the binary Hg−Te aggregates, and compounds [Mn(trien) (Hg2Te4)]n (D) and [Zn(trien) (Hg2Te4)]n (E) are the first examples of telluromercurates incorporated with TM complex fragments. Optical Properties. The solid-state near-IR/UV−vis reflectance spectroscopies of A−F were measured on powder samples at room temperature. The absorption data from the reflectance spectroscopy by the Kubelka−Munk function27 demonstrate that the compounds A−F show well-defined abrupt absorption edges with estimated band gaps (Eg) at 1.04, 1.05, 1.06, 0.96, 0.98, and 1.09 eV (Figure 10), respectively,

Photocatalytic Properties. The photocatalytic performance of Mn(II) complexes (A, C, D) were evaluated by the degradation of CV in aqueous solution under visible-light irradiation at room temperature. In a typical reaction, 30 mg samples were mixed with 40 mL of CV solution (1 × 10−5 mol· L−1) and stirred in the dark for 30 min to establish the adsorption equilibrium between catalyst and solution. Then, the mixture was exposed to visible-light irradiation for photodegradation under stirring. The concentration changes of CV were monitored by examining the variations of intensities in the maximal absorption in UV−vis spectra at 583.3 nm. The photocatalytic activity is expressed by the C/C0 via time, where C is the CV concentration at the different reaction time, and C0 is the initial concentration of CV after the adsorption equilibrium. For comparison, the photodegradation of CV without catalyst was also performed under the same conditions. As shown in Figure 11, the photolysis of CV without catalyst under visible-light irradiation was negligible. In compounds A, C, and D, C exhibits the highest photocatalytic activity toward CV degradation. The degradation ratio of CV over 3 reaches 92% after exposure to visible light for 12 h (Figure 11). The polymeric compounds A and D show moderate photocatalytic activity for CV degradation with the degradation ratio of 56% and 62%, respectively (Figure 11 and Figure S24), and they are less effective for CV degradation than compound C with a cluster structure. The tellurides A, C, and D exhibit less photocatalytic activity than the Mn−Ga−Sn sulfide Mn2Ga4Sn4S20[Mn2(en)5]2·4H2O in the degradation of CV (100% degradation in 1.5 h).38 After photocatalytic reactions, the catalysts were filtered, and were measured using PXRD. The PXRD patterns show that A, C, and D kept good crystallinity after photocatalytic reactions (Figures S7, S9, and S10). Thermal Properties. Thermal stabilities of compounds A− F were investigated by TGA under a nitrogen atmosphere in the temperature range of 25−500 °C (Figure S25). TGA curve reveals that compound A decomposes in two steps with total mass losses of 17.4% (Figure S25a). The total mass loss is in accordance with the removal of four N2H4 molecules (calcd 5.5%) between 205 and 230 °C in the first step, and two trien ligands (calcd: 12.4%) between 240 and 265 °C in the second step. Compounds B and C exhibit similar two-step thermal decomposition processes with total mass losses of 17.0% and 15.7%, respectively (Figures S25b,c). Compounds D−F decompose in a single step with starting temperature at ∼260

Figure 10. Solid-state optical absorption spectra of A−F.

which suggest that compounds A−F are semiconductors with narrow gaps. The absorption is likely due to charge-transfer transitions from a filled valence band of telluride anions to a mainly Hg2+-based empty conduction band. These band gaps exhibit blue shifts compared with that of the rubidium mercury telluride Rb4Hg5Te13 (Eg = 0.8 eV).37 They are lower than the band gap of ternary Hg-tellurostannate cluster [K10(H2O)20][Hg4(μ4-Te) (SnTe4)4] (Eg = 1.39 eV)].36a

Figure 11. (a) Time-dependent absorption spectra of CV degradation by using compound C photocatalyst. (b) Concentration evolution of CV in the presence of compounds A, C, and D under exposure to visible-light. H

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Inorganic Chemistry °C for D and E, and 285 °C for F (Figures S25d−f). The mass losses of 12.8%, 12.2%, and 12.7% are consistent with the complete removals of the amino ligands (calcd: 13.1% for D, 13.0% for E, and 12.4% for F).

2010, 49, 7331−7339. (b) Jariwala, B.; Voiry, D.; Jindal, A.; Chalke, B. A.; Bapat, R.; Thamizhavel, A.; Chhowalla, M.; Deshmukh, M.; Bhattacharya, A. Synthesis and characterization of ReS2 and ReSe2 layered chalcogenide single crystals. Chem. Mater. 2016, 28, 3352− 3359. (2) (a) Nguyen, S. L.; Malliakas, C. D.; Francisco, M. C.; Kanatzidis, M. G. Lattice-matched transition metal disulfide intergrowths: the metallic conductors Ag2Te(MS2)3 (M = V, Nb). Inorg. Chem. 2013, 52, 6520−6532. (b) Li, H.; Malliakas, C. D.; Liu, Z.; Peters, J. A.; Jin, H.; Morris, C. D.; Zhao, L.; Wessels, B. W.; Freeman, A. J.; Kanatzidis, M. G. CsHgInS3: A new quaternary semiconductor for γ ray detection. Chem. Mater. 2012, 24, 4434−4441. (c) Malavasi, L.; Margadonna, S. Structure−properties correlations in Fe chalcogenide superconductors. Chem. Soc. Rev. 2012, 41, 3897−3911. (d) Kehoe, A. B.; Scanlon, D. O.; Watson, G. W. The electronic structure of sulvanite structured semiconductors Cu3MCh4 (M = V, Nb, Ta; Ch = S, Se, Te): prospects for optoelectronic applications. J. Mater. Chem. C 2015, 3, 12236− 12244. (3) (a) Teo, M. Y. C.; Kulinich, S. A.; Plaksin, O. A.; Zhu, A. L. Photoinduced structural conversions of tansition metal chalcogenide materials. J. Phys. Chem. A 2010, 114, 4173−4180. (b) Falkowski, J. M.; Surendranath, Y. Metal chalcogenide nanofilms: platforms for mechanistic studies of electrocatalysis. ACS Catal. 2015, 5, 3411− 3416. (c) Kershaw, S. V.; Susha, A. S.; Rogach, A. L. Narrow bandgap colloidal metal chalcogenide quantum dots: synthetic methods, heterostructures, assemblies, electronic and infrared optical properties. Chem. Soc. Rev. 2013, 42, 3033−3087. (4) (a) Manos, M. J.; Kanatzidis, M. G. Highly efficient and rapid Cs+ uptake by the layered metal sulfide K2xMnxSn3−xS6 (KMS-1). J. Am. Chem. Soc. 2009, 131, 6599−6607. (b) Zhao, W.; Zhang, C.; Geng, F.; Zhuo, S.; Zhang, B. Nanoporous hollow tansition metal chalcogenide nanosheets synthesized via the anion-exchange reaction of metal hydroxides with chalcogenide ions. ACS Nano 2014, 8, 10909−10919. (5) Xia, C.; Alshareef, H. N. Self-templating scheme for the synthesis of nanostructured tansition-metal chalcogenide electrodes for capacitive energy storage. Chem. Mater. 2015, 27, 4661−4668. (6) (a) Shim, Y.; Young, R. M.; Douvalis, A. P.; Dyar, S. M.; Yuhas, B. D.; Bakas, T.; Wasielewski, M. R.; Kanatzidis, M. G. Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) centers. J. Am. Chem. Soc. 2014, 136, 13371−13380. (b) Huang, Z. J.; Luo, W. J.; Ma, L.; Yu, M. Z.; Ren, X. D.; He, M. F.; Polen, S.; Click, K.; Garrett, B.; Lu, J.; Amine, K.; Hadad, C.; Chen, W. L.; Asthagiri, A.; Wu, Y. Y. Dimeric [Mo2S12]2− cluster: a molecular analogue of MoS2 edges for superior hydrogen-evolution electrocatalysis. Angew. Chem. 2015, 127, 15396−15400. (7) (a) Mitchell, K.; Ibers, J. A. Rare-earth transition-metal chalcogenides. Chem. Rev. 2002, 102, 1929−1952. (b) Wood, P. T.; Pennington, W. T.; Kolis, J. W.; et al. Inorganic synthesis in supercritical amines: synthesis of [W4S8S(H2NCH2CH2NH2)]4S, containing an isolated sulfide ion. Inorg. Chem. 1993, 32, 129−130. (c) Li, J.; Nazar, L. F. Mesostructured iron sulfides. Chem. Commun. 2000, 18, 1749−1750. (d) Gougeon, P.; Potel, M.; et al. Syntheses and structural, physical, and theoretical studies of the novel isostructural Mo9 cluster compounds Ag2.6CsMo9Se11, Ag4.1ClMo9Se11, and hMo9Se11 with tunnel structures. Inorg. Chem. 2004, 43, 1257−1263. (e) Brandmayer, M. K.; Clérac, R.; Weigend, F.; Dehnen, S. Orthochalcogenostannates as ligands: syntheses, crystal structures, electronic properties, and magnetism of novel compounds containing ternary anionic substructures [M4(μ4-Se) (SnSe4)4]10− (M = Mn, Zn, Cd, Hg)∞3{[Hg4(μ2-Se) (SnSe4)3]6−}, or ∞1{[HgSnSe4]2−}. Chem. - Eur. J. 2004, 10, 5147−5157. (f) Mitzi, D. B. N4H9Cu7S4: a hydraziniumbased salt with a layered Cu7S4-framework. Inorg. Chem. 2007, 46, 926−931. (g) Fuhr, O.; Dehnen, S.; Fenske, D. Chalcogenide clusters of copper and silver from silylated chalcogenide sources. Chem. Soc. Rev. 2013, 42, 1871−1906. (h) Stacey, T. E.; Borg, C. K. H.; Zavalij, P. J.; Rodriguez, E. E. Magnetically stabilized Fe8(μ4-S)6S8 clusters in Ba6Fe25S27. Dalton Trans. 2014, 43, 14612−14624.

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CONCLUSION We have developed a facile and effective N2H4-assisted solvothermal route for the synthesis of crystalline polynuclear telluromercurates containing TM complex cations. The TMtelluromercurates A−F had been conveniently prepared by onepot synthesis using Te powder as the sole tellurium source with the assistance of N2H4 in trien and tepa polyamine solutions in lower temperature range. The novel polymeric 1D [Hg2Te42−]n and [Hg5Te124−]n chains in D−F represent new species of the binary telluromercurate aggregates. With tetradentate trien as the chelating ligand to the TM(II) ions, the Hg−Te binary anions coordinating to the TM(II) centers were obtained for the first time in compounds D and E. This observation indicates the important influence of polyamino denticities on coordination chemistry of the telluromercurate anions. Compound C exhibits effective photocatalytic activity toward CV degradation. It is expected that this N2H4-assisted solvothermal method may also be extended to the syntheses of other tellurometalates.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b00115. Selected bond lengths and angles for A−F, IR spectra, PXRD patterns, structural figures, time-dependent absorption spectra of CV degradation in photocatalysis, and TG curves (PDF) Accession Codes

CCDC 1546480−1546485 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Dingxian Jia: 0000-0003-3212-8407 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of P. R. China (No. 21171123), the project funded by the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions, and the Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow Univ.

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REFERENCES

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Inorganic Chemistry

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DOI: 10.1021/acs.inorgchem.7b00115 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.7b00115 Inorg. Chem. XXXX, XXX, XXX−XXX