Syntheses, Crystal Structures and Optoelectronic Properties of Two New Inorganic Thioantimonates①

LI Ji-Long MA Wen JIN Jian-Ce FENG Mei-Ling HUANG Xiao-Ying

Syntheses, Crystal Structures and Optoelectronic Properties of Two New Inorganic Thioantimonates①

LI Ji-Longa, bMA WenbJIN Jian-CebFENG Mei-Lingb②HUANG Xiao-Yingb

a(College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China)b(State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China)

Two new thioantimonates, (NH4)2Sb10S16(1) and K1.4(NH4)0.6Sb10S16(2), have been synthesized by solvothermal method with the yields of 80% and 85%, respectively.Single-crystal X-ray diffraction (SCXRD) study reveals that 1 crystallizes in the monoclinic space group ofwith= 8.1284(4),= 19.4587(9),= 9.1030(4) ?,= 91.736(5)°,= 1439.14(12) ?3,= 2,D= 4.077 g·cm-3,(000) = 1576,= 10.389 mm-1,= 0.0343 and= 0.0624 (> 2()); 2 also crystallizes in the monoclinic space group ofwith= 8.0989(6),= 19.3730(17),= 9.0411(6) ?,= 91.879(6)°,= 1417.79(19) ?3,= 2,D= 4.207 g·cm-3,(000) = 1598,= 10.748 mm-1,= 0.0323 and= 0.0664 (> 2()).The anionic frameworks of two compounds both feature two-dimensional (2) [Sb10S16]2n-layers.The stabilities and optoelectronic properties of 1 and 2 have been characterized.In particular, they are stable under acidic or alkaline conditions (pH = 0 or 12.5), showing excellent acid-based resistance.

solvothermal synthesis, crystal structure, thioantimonates, optoelectronic property;

1 INTRODUCTION

Metal sulfides have received widespread attention because of their fascinating structural diversities, and potential applications in catalysis[1, 2], ion exchange[3, 4], nonlinear optics[5], semiconductors[6], optoelectronics[7-9],.Among them, thioantimonates(III) have been extensively studied due to the stereochemical effect of lone-pair electrons on Sb(III), by which Sb(III) can form various coordination geometries of [SbS] (= 3～6), such as [SbS3][10], [SbS4][10], [SbS5][11]and [SbS6][12, 13].These different structural units can be further polymerized to form a series of anionic polymeric moieties of [SbS]3x-2y(, [Sb4S7]2n-, [Sb5S8]-, [Sb5S9]3n-, [Sb8S13]2n-and [Sb9S15]2n-) with diverse dimensionalities by corner-sharing, edge-sharing, or face-sharing[14-21].

In recent decades, a large number of metal sulfides have been synthesized and prepared by high temperature solid state reactions[22, 23], molten salt reactions[24], reactions in deep eutectic solvents[25-27], solvothermal methods[13, 28-31], and so on.Among these synthetic methods, solvothermal methods have been proved to be very effective for the preparation of thioantimonates(III).Up to now, thioantimonates(III) with metal cations (, K+, Cs+, Ba2+, Sr2+and Tl+)[11, 20, 32-34]or protonated organic amines (, [Me4N]+, [Et4N]+and [MeNH3]+)[10, 13-19]as charge-balancing agents have been extensively reported, such as (dienH2)[Sb8S13]·1.5H2O[35], (1,2-dapH)2[Sb8S13][35], (CH3NH3)2Sb8S13[18], [C8N4H26]0.5[Sb7S11][36], Cs2Sb4S7[37], SrSb4S7·6H2O[[33]and BaSb2S4[32].

It is also worthy to note that the anions [Sb5S8]2-or [Sb10S16]2-with the Sb:S ratio of 1:1.6 are particularly prevalent in thioantimonates(III) whose cations are usually protonated organic amines or inorganic ions, such as ASb5S8(A = K, Tl)[11], (C3H12N2)[Sb10S16] ([C3H12N2]2+= doubly protonated N,N-diethylethylenediamine)[38], [C6H17N3]Sb10S16([C6H17N3]2+= doubly protonated 2-piperazine-N-ethylamine cation)[18], [H3N(CH2)3NH3]Sb10S16([H3N(CH2)3NH3]2+= doubly protonated 1,3-propanediamine)[39], [C6H18N2]Sb10S16·H2O ([C6H18N2]2+= doubly protonated 1,2-diaminopropane)[40].However, it is rare for NH4+to be introduced into thioantimonates(III) as charge-balancing agent to form the polymeric anions of [SbS]except NH4Sb4S7[41]and NH4SbS2[42].Herein, we report two 2thioantimo- nates(III) synthesized by the mild solvothermal reactions, namely (NH4)2Sb10S16(1) and K1.6(NH4)0.4Sb10S16(2), which contain NH4+and the mixed cations of NH4+and K+as the charge-balancing agents, respectively.Their crystal structures, stabilities and optoelectronic properties were studied.

2 EXPERIMENTAL

All reagents and chemicals employed in this study were analytical reagents and commercially available without further purification.Single-crystal X-ray diffraction (SCXRD) data for 1 and 2were collected by using graphite-monochromatized Mo-radiation (= 0.71073 ?) at 100 K on an Agilent Supernova Dual diffractometer with an Atlas detector.Elemental analyses (EA) of H, N and S were obtained by using a German Elementary Vario MICRO instrument.Solid-state ultraviolet-visible (UV-Vis) spectra were analyzed at room temperature with BaSO4as a standard (100% reflectance) using a Shimadzu UV-2600 spectrometer spectrophotometer.PowderX-ray diffraction(PXRD) measurement was performed at room temperature on a Miniflex II diffractometer at 30 kV, 15 mA using Curadiation (= 1.54178 ?) in the angular range of 2= 5～50° or 5～55°.Thermogravimetric analyses (TGA) were performed with a NETZSCH STA449C thermo- gravimetric analyzer at a heating rate of 10 ℃·min-1under a nitrogen atmosphere.

2.1 Synthesis of (NH4)2Sb10S16 (1)

A mixture of Sb(Ac)3(0.5 mmol) and S (1.5 mmol) in a mixed solvent of 3 mL NH3·H2O and 0.5 mL N2H4·H2O was sealed in a 20 mL Teflon-lined stainless-steel reactor and heated at 180 ℃ for 5 days.Then the product was washed with distilled water and ethanol and then dried in air.The dark-red plate-like crystals of 1 were obtained with a high yield (71 mg, 80% based on Sb(Ac)3).EA, calcd.: H, 0.46; N, 1.59; S, 29.04%.Found: H, 0.36; N, 1.64; S, 28.96%).

2.2 Synthesis of K1.4(NH4)0.6Sb10S16 (2)

A mixture of KCl (1.6 mmol), Sb(Ac)3(0.5 mmol) and S (1.5 mmol) in a mixed solvent of 2 mL NH3·H2O and 1 mL N2H4·H2O was sealed in a 20 mL Teflon-lined stainless-steel reactor and heated at 180 ℃ for 5 days.After that, the product was washed with distilled water and ethanol and then dried in air.The dark-red plate-like crystals of 2 were obtained with a high yield (77 mg, 85% based on Sb(Ac)3).EA, calcd.: H, 0.13; N, 0.47; S, 28.56%.Found: H, < 0.3; N, 0.51; S, 28.76%).

2.3 Structure refinements

The dark-red plate-like crystals 1 and 2 were selected for the diffraction experiment with dimensions of 0.20mm × 0.10mm × 0.02mm and 0.20mm × 0.05mm × 0.02mm, respectively.For 1, a total of 11812 reflections were collected in the range of 3.331°≤≤31.200° withint= 0.0402, of which 6555 are independent.Crystal1crystallizes in the monoclinicspace groupwith:= 8.1284(4),= 19.4587(9),= 9.1030(4) ?,= 91.736(5)°,= 1439.14(12) ?3,= 2,D= 4.077 g·cm-3,(000) = 1576,= 10.389 mm-1,= 0.0343 and= 0.0624 (> 2().A total reflections of 9746 were collected in 2 in the range of 10.2°≤≤29.634°withint= 0.0376, 5225 of which are independent.Crystal2is also of monoclinicspace group with= 8.0989(6),= 19.3730(17),= 9.0411(6) ?,= 91.879(6)°,= 1417.79(19) ?3,= 2,D= 4.207 g·cm-3,(000) = 1598,= 10.748 mm-1,= 0.0323 and= 0.0664 (> 2()).2018 package was used to solve and refine the structure on2by the full-matrix least-squares methods[43].Selected bond lengths and bond angles of 1 and 2 are shown in Tables 1 and 2, respectively, and selected hydrogen bonds are listed in Table 3.

Table 1. Selected Bond Lengths (?) for 1 and 2

Compound 1: Symmetry transformations: #1:–1,,+1; #2:+1/2, –+1,–1/2; #3:–1/2, –+2,+1/2;

Compound 2: Symmetry transformations: #1:–1,,+1; #2:+1/2, –+1,–1/2; #3:,,–1;

Table 2. Selected Bond Angles (°) for 1 and 2

Compound 1: Symmetry transformations: #1:–1,,+1; #2:+1/2, –+1,–1/2; #3:–1/2, –+2,+1/2;#4:+1/2, –+2,–1/2; #5:+1,,–1; #6:–1/2, –+1,+1/2.

Compound 2: Symmetry transformations: #1:–1,,+1; #2:+1/2, –+1,–1/2;#4:–1/2, –+2,+1/2; #6:+1/2, –+2,–1/2; #7:+1,,–1;–1/2, #8:–1/2, –+1,+1/2;

Table 3. Selected Hydrogen Bond Lengths (?) and Bond Angles (°) for 1 and 2

Compound 1: Symmetry transformations: #3:–1/2, –+2,+1/2;#6:–1/2, –+1,+1/2; #7:+1/2, –+1,+1/2; #8:,,+1.Compound 2: Symmetry transformations: #4:–1/2, –+2,+1/2;#8:–1/2, –+1,+1/2; #9:,,+1; #10:+1/2, –+1,+1/2

2.4 Acid-base resistance experiment

30 mg sample (1 or 2) was placed in a 20 mL glass bottle with 15 mL acidic (pH = 0) and alkaline (pH = 12) solution, respectively, which was stirred vigorously for 10 h.Then the mixture was separated into solid and liquid, and the separated solid products were washed with water and ethanol.

2.5 Electrochemical experiment

5 mg sample (1 or 2) was placed in a sample tube with 0.2 mL water, which was sequentially added by 40 uL anhydrous ethanol and 10 uL naphthol.The mixture was sonicated and shaken in an ultrasonic system for 8 h.Then 50 uL of the mixture was deposited on a 1×4 cm2conductive glass with a sample deposition area of 1×1 cm2, which was used as a photoanode.Finally, electroche- mical experiments were performed in a three-electrode system via an electrochemical workstation using 0.5 M sodium sulfate salt solution as the electrolyte.

3 RESULTS AND DISCUSSION

3.1 Discussion on synthesis and crystal structures

1 and 2 were synthesized by the solvothermal method.1 could be easily obtained by mixing 0.5 mmol Sb(Ac)3and 1.5 mmol S in the mixed solvents of 3 mL NH3·H2O and 0.5 mL N2H4·H2O, while 2 was afforded by a similar reaction except that the additional reagent KCl (1.6 mmol) was added, and the amount of solvents was adjusted to 2 mL NH3·H2O with 1 mL N2H4·H2O.In the synthesis of 2, if KCl was replaced with K2CO3or the amount of S exceeded 1.5 mmol, the by-production (NH4)2Sb4S7would be generated.Therefore, KCl plays an important role in the synthesis of 2.In addition, the crystals of 1 and 2 could not be obtained without N2H4·H2O.Therefore, the presence of N2H4·H2O in the reaction processes was necessary.

SCXRD analyses show that 1 and 2 crystallizein monoclinic space group.Their asymmetric units both contain ten unique Sb sites and sixteen S sites, but two [NH4]+in 1 and 1.4 K+and 0.6 [NH4]+in 2(Fig.1a).Since the two compounds are isomorphic, only the structure of 1 was analyzed in detail.As shown in Figs.1b and 1c, the anionic layer of [Sb10S16]2-consists of three different coordination modes of Sb(III), namely [SbS3] (for Sb(1), Sb(3), Sb(4), Sb(7), Sb(8) and Sb(10)), [SbS4] (for Sb(5), Sb(6) and Sb(9)), and [SbS5] (for Sb(2)).Then the Sb(9)S4and Sb(10)S3units are jointed together via corner-sharing to form a binuclear [Sb2S5] cluster.Sb(3)S3and Sb(5)S4or Sb(5)S4and Sb(6)S3units also form the binuclear [Sb2S5] cluster.Sb(9)S4, Sb(1)S3and Sb(2)S5units are connected together via corner-sharing to form a trinuclear [Sb3S7] cluster; Sb(6)S4, Sb(7)S3and Sb(8)S3units are jointed together via corner-sharing to get a trinuclear [Sb3S7] cluster; Sb(2)S5, Sb(3)S3and Sb(4)S3units are linked together by corner-sharing to give a trinuclear [Sb3S8] cluster.Then, three [Sb2S5], two [Sb3S8] and one [Sb3S7] units are assembled by corner-sharing into a waved [Sb10S16]2n-anionic layer(Fig.1c).As shown in Tables 1 and 2, the Sb?S bond lengths scatter over a range from 2.399 to 2.926 ? and corresponding S?Sb?S angles are in the range of 78.65～175.40°.Their bond lengths and angles are comparable tothose of reported polymeric anions [Sb5S8]2-or [Sb10S16]2-in the literature[11, 18, 38-40].Additionally, the NH4+cations are located at the interlayer space of anionic layers, which interact with two adjacent [Sb10S16]2n-layers through N?H···S bonds, resulting in a three-dimensional supramole- cular network (Figs.1d, 2e and 2f).From Fig.1 and Table 3, N?H···S hydrogen bonds are found in the range of 3.198(10)～3.475(10) ?, and N?H···S angles vary from 112.3oto 163.0oin 1 (Table 3).

Fig.1. (a) Asymmetric unit of (NH4)2Sb10S16; (b) Coordination modes of [SbS3], [SbS4] and [SbS5] in [Sb10S16]; (c) 2anionic layer of [Sb10S16]2n-viewed along the-axis (The red and blue polyhedra represent [SbS4] and [SbS5], respectively); (d) a three-dimensional supramolecular network formed by N?H···S bonds between NH4+cations and [Sb10S16]2n-anionic layer; the N?H···S bonds of N(1)?H···S (e) and N(2)?H···S (f)

Theanionic [Sb10S16]2n-layers of 1 and 2 resemble that of ASb5S8(A = K, Tl)[11]with the same space group of.The [Sb10S16]2n-anionic layers have also been found in[C6H17N3]Sb10S16[18], (C3H12N2)[Sb10S16][38], [H3N(CH2)3NH3]Sb10S16[39]and [C6H18N2]Sb10S16·H2O[40](Table 4).However, these compounds present distinct cell parameters and crystallize in three types of space groups,that is, type I:for compounds 1,2 and ASb5S8(A = K, Tl); type II:21/for [C6H17N3]Sb10S16and [C6H18N2]Sb10S16·H2O; type III:21/for (C3H12N2)[Sb10S16]and [H3N(CH2)3NH3]Sb10S16.If considering the additional secondary Sb?S interactions in interlayers, the above [Sb10S16]2n-layers can be defined as 3structures.As shown in Fig.2, the type I [Sb10S16]2n-layer features unique units of six [SbS3], three [SbS4] and one [SbS5] (Fig.2a); type II [Sb10S16]2n-layer includes unique units of nine [SbS3] and one [SbS4] (Fig.2b); type III [Sb10S16]2n-layer contains [SbS3] units only (Fig.2c).Fig.2 clearly shows the difference of tortuosity of anionic layer in the three types of [Sb10S16]2n-layers.

Table 4. Comparison of Crystal Parameters of 1 with Other Thioantimonates with the Sb:S Ratio of 1:1.6

S.G.= space group; [C6H17N3]2+= doubly-protonated 2-piperazine-N-ethylamine; [C6H18N2]2+= doubly-protonated 1,2-diaminopropane; [C3H12N2]2+= doubly-protonated,-diethylethylenediamine; [H3N(CH2)3NH3]2+= doubly-protonated 1,3-propanediamine

Fig.2. Comparison of anionic layers for 1 (a), [C6H17N3]Sb10S16(b) and (C3H12N2)Sb10S16(c)

3.2 Powder X-ray diffraction patterns, TG and UV-vis spectra

As shown in Fig.3a, PXRD patterns for 1 and 2 match well with their corresponding simulated ones, indicating the phase-purity.In addition, the two compounds were added to acidic (pH = 0) and alkaline (pH = 12) solutions in order to investigate their acid-base resistances.1 and 2 are stable even under acidic or basic solutions by comparing the PXRD patterns of pristine compounds and soaking products (Fig.3b).The results confirm that the 2anionic layer of [Sb10S16]2n-can be maintained under strong acidic and alkaline conditions, thus indicating good acid and base resistances for both compounds.

Fig.3. (a) Simulated and experimental PXRD patterns of 1 and 2; (b) PXRD patterns of the pristine 1 and 2 and their corresponding products soaked in the acidic or alkaline solutions for 10 h

The thermal stabilities of 1 and 2 were studied by TGA in a N2atmosphere from 30 to 800 ℃.TG curves are shown in Fig.5a.They show the weight loss of 4.05% from 30 to 325 ℃ for 1 (the theoretical value of 3.96%) and 1.18% from 30 to 330 ℃ for 2 (the theoretical value of 1.17%), corresponding to the escape of NH3and H2S molecules, respectively.The optical absorption edges of 1 and 2 are 1.82 and 1.79 eV, respectively, falling in the range for semiconductor materials (Fig.5b).Apparently, the lower optical absorption edge of 1 than that of 2 is consistent with its darker color than that of 2 (Fig.5b).

Fig.4. TG curve (a) and optical absorption spectra (b) of compounds 1 and 2.Insert image: photograph of a single-crystal for compounds 1 and 2

3.3 Photoelectric properties

The photoelectric properties of 1 and 2 were investigated by measuring their photocurrent responses under visible light irradiation (≥ 420 nm) using a standard three-electrode system.From Fig.5, the rapid and consistent photocurrent responses of 1 and 2 were performed in a multiple 10 sec switching period under visible light irradiation.2 exhibits a stronger transient photocurrent response, which is about twice that of 1.It can be confirmed that 2 has higher photogenerated electron transfer efficiency and photogenerated electron-hole pairs separation efficiency than 1 under visible light irradiation[44].Meanwhile, the repeatable anodic photocurrent responses indicate that 1 and 2 belong to-type (electron- conducting) semiconductor[45, 46].

Fig.5. Photocurrent responses of 1 and 2 under visible light irradiation (≥ 420 nm)

4 CONCLUSION

In conclusion, two new thioantimonates(III) were synthesized by a simple solvothermal method, and their structures, stabilities and optoelectronic properties were studied.They have the same anionic layer of [Sb10S16]2n-.The acquisition of 2 could be simply achieved by adding KCl during the preparation of 1.The stability experiments indicate that 1 and 2 have excellent thermal stability and acid-based resistances.The photoelectric results and optical absorption spectra confirm that 1 and 2 aresemiconductors and 2 shows better photoelectric property than 1.The current compounds enrich the structural diversity of thioantimonates(III), especially thioantimonates(III) with NH4+cations.The synthetic route described in this work should be an effective way to prepare novel thioantimonates.

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21 December 2020;

21 January 2021 (CCDC 2051501 for 1 and 2051502 for 2)

①This research was supported by the National Science Foundations of China (Nos.22076185 and 21771183), the Natural Science Foundation of Fujian Province (No.2020J06033) and FJIRSM&IUE Joint Research Fund (No.RHZX-2018-005)

.E-mail: fml@fjirsm.ac.cn

10.14102/j.cnki.0254–5861.2011–3075