Syntheses, Crystal Structures, and Optical and Photocatalytic

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Syntheses, Crystal Structures, Optical and Photocatalytic Properties of Four Small-Amine-Molecule-Directed M-Sn-Q (M = Zn, Ag; Q = S, Se) Compounds Bo Zhang, Mei-Ling Feng, Jun Li, Qianqian Hu, XingHui Qi, and Xiao-Ying Huang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01619 • Publication Date (Web): 17 Jan 2017 Downloaded from http://pubs.acs.org on January 18, 2017

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Crystal Growth & Design

Syntheses, Crystal Structures, Optical and Photocatalytic Properties of Four Small-AmineMolecule-Directed M−Sn−Q (M = Zn, Ag; Q = S, Se) Compounds Bo Zhang,†, ‡ Mei−Ling Feng,† Jun Li,†, ‡ Qian−Qian Hu,† Xing−Hui Qi,† and Xiao−Ying Huang*, †

†

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People’s Republic of China ‡

University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China

ABSTRACT: By utilizing different small amine molecules as structure-affecting agents (SAAs) and charge-balancing agents (CBAs), four new M−Sn−Q (M = Zn, Ag; Q = S, Se) compounds with the anionic architectures ranging from one-dimensional (1D) chain to three-dimensional (3D) network have been solvothermally synthesized. Compound [(Me)2NH2]2ZnSn3Se8 (1) features an anionic (4,4) layer of [ZnSn3Se8]n2n– and represents a rare [ZnSn3Se10] T2 clusterbased 2D Zn−Sn−Se compound directed by organic amine. Compound [NH4]3AgSn3Se8 (2)

ACS Paragon Plus Environment

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contains

infinite

linear

anionic

chains

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[AgSn3Se8]n3n–.

of

Compound

[CH3NH3]2[H3O]Ag5Sn4Se12·C2H5OH (3) exhibits a 3D open-framework structure of [Ag5Sn4Se12]n3n– with intersecting 3D channels. Compound [CH3NH3]6Ag12Sn6S21 (4) features a 3D framework structure with 1D channels filled by [CH3NH3]+ cations. The most fascinating structural feature of compound 4 is that there exists a complex 3D [Ag12S17]n22n− anionic network based on the combination of three types of basic building blocks of [AgS2] dumbbells, [AgS3] triangles and [AgS4] tetrahedra. The thermal stabilities, optical properties of the title compounds 1−4, as well as the theoretical band structure and density of states (DOS) of compound 4 have been studied. Moreover, compound 3 displayed visible-light-driven photocatalytic activity for degradation of crystal violet (CV).

INTRODUCTION Extensive research interest has been focused on chalcogenidometalates, stemming not only from their fascinating structures, but also their potential applications in many areas such as ion exchange,1−4

photocatalysis,5

fast-ion

conduction,6

and

nonlinear

optics.7

The

chalcogenidometalates containing group 14 metal ion Sn4+ have received considerable attention owing to the flexible coordination behavior of Sn to chalcogen Q2− (Q = S, Se, Te), and diverse self-condensation ways of [SnQn] polyhedra.8−18 Recently, an effective strategy for the development of new chalcogenidometalates is to design and construct new heterometallic secondary building units (SBUs) by the combination of different polyhedra of Sn and a second metal ion (typically transition metal ions).19−21 Such a synthesis strategy not only may result in


2

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numerous heterometallic chalcogenidometalates with structural and compositional diversities but also

may

engender

interesting

properties.22−29

For

instance,

the

compound

[Zn(H2O)4][Zn2Sn3Se9(CH3NH2)]22 exhibited a strong second harmonic generation response, while the compound [(Me)2NH2]0.75[Ag1.25SnSe3]24 showed interesting cation-exchange properties with the specificity for Cs+ ion. Mild solvothermal techniques have proven to be very effective routes for the preparation of chalcogenidometalates, in which the amines molecules were often applied as reactive medium and/or SAAs.17−21 In the preparation of M−Sn−Q (M = transition metal ions), the polyamine (e.g. ethylendiamine (en) and diethylenetriamine (dien)) or large organic amine molecules (e.g. N-(2aminoethyl)piperazine (AEP) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)) have been widely used as the solvents and/or SAAs.23,30−44 By contrast, the smaller organic amine (e.g. [CH3NH3]+ and [(Me)2NH2]+) or NH4+-directed M−Sn−Q compounds are rarely explored. The limited examples include [CH3NH3]2xMnxSn3−xS6·0.5H2O (x = 0.5−1.1),45 [CH3NH3]2Ag4SnIV2SnIIS8,46 [NH4]2Ag6Sn3S10,47 [NH4]4Ag12Sn7Se22,48 and [(Me)2NH2]0.75Ag1.25SnSe3.24 Since 2008, our group started to explore the solvothermal syntheses of small organic amine-directed heterometallic chalcogenidometalates based on the combination of p-block metal ions, for instance, the integration of Sb(III) with group 14/13 metal ions (Ge4+, Sn4+, Ga3+, In3+).2,4,49−53 Indeed, our attempts resulted in many heterometallic chalcogenidometalates with intriguing architectures that might not be obtained upon the structural direction of the polyamine or large organic amines. Furthermore, some of these compounds exhibited interesting ion-exchange and photocatalytic properties.2,4,50,51 As a systematic extension of our previous work, herein, we successfully prepared and structurally characterized four new M−Sn−Q (M = Zn, Ag; Q = S, Se) compounds,

namely,

[(Me)2NH2]2ZnSn3Se8

(1),

[NH4]3AgSn3Se8

(2),


3


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[CH3NH3]2[H3O]Ag5Sn4Se12·C2H5OH (3) and [CH3NH3]6Ag12Sn6S21 (4). Compound 1 features a 2D anionic layer of [ZnSn3Se8]n2n– and compound 2 consists of an infinite linear [AgSn3Se8]n3n– anionic chain. Compound 3 possesses a 3D [Ag5Sn4Se12]n3n– anionic framework, while compound 4 features a 3D open-framework structure of [Ag12Sn6S21]n6n– that is constructed by a complex 3D [Ag12S17]n22n− anionic network decorated by [Sn2S7] dimers. Interestingly, compound 3 showed photocatalytic degradation activity over crystal violet (CV) under visible light irradiation. The thermal stabilities and optical properties of the title compounds 1−4, and theoretical band structure and density of states (DOS) of compound 4 have also been studied.

EXPERIMENTAL SECTION Materials and Methods. Methylamine (33−40% alcohol solution) was purchased from Aladdin Company (Shanghai, China), selenium powder (99.9%) was received from Yingda Rare Chemical Regents Factory (Tianjin, China), and other reagents such as formamide (99.3%), dimethylamine (33−40% aqueous solution) and hydrazine hydrate (80%) were obtained from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). All starting chemicals were analytical grade and were used as received without further purification. Elemental analyses (EA) of C, H, and N were performed using a German Elementary Vario EL III instrument. Energy-dispersive spectroscopy (EDS) was recorded on a JEOL JSM-6700F scanning electron microscope. Room-temperature optical diffuse reflectance spectra of powder samples were obtained using a UV−vis−NIR Varian 86 Cary 500 Scan spectrophotometer. Absorption (α/S) data were calculated from reflectance using the Kubelka−Munk function α/S = (1 − R)2/2R, where α is the absorption coefficient, S is the scattering coefficient which is


4

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practically independent of wavelength when the particle size is larger than 5 µm, and R is the reflectance.54 Thermogravimetric analyses (TGA) were carried out with a NETZSCH STA449C at a heating rate of 10 °C/min under a nitrogen atmosphere. Powder X-ray diffraction (PXRD) patterns were collected at room temperature on a Miniflex II diffractometer using CuKα radiation (λ = 1.5406 Å) in the 2θ range of 5−65°. The supernate of photocatalytic experiment was analyzed with the help of UV−vis absorption spectra instrument (SHIMADZU UV-2600 UV−vis spectrometer). Synthesis of the precursor AgCl. Starting materials of AgNO3 (3.397 g, 20.0 mmol) and NaCl (1.402 g, 24.0 mmol) were dissolved in 100 mL and 50 mL distilled water, respectively. The two aqueous solutions were mixed at room temperature under magnetic stirring. White powders were obtained by filtration in the dark, washed several times with distilled water and ethanol (99.7%) and dried under vacuum (Yield: 2.345 g, 82% based on AgNO3). Synthesis of [(Me)2NH2]2ZnSn3Se8 (1). A mixture of Zn (0.033 g, 0.5 mmol), Sn (0.178 g, 1.5 mmol), Se (0.316 g, 4.0 mmol), dimethylamine (33−40% aqueous solution, 3.0 mL) and methanol (99.5%, 3.0 mL) was stirred under ambient conditions until homogeneous. The resulting mixture was sealed into a 20 mL Teflon–lined stainless–steel autoclave, and heated at 190 °C for 7 days, and then cooled to room temperature naturally. After isolation, a mixture of unidentified yellow powders and orange sheet-like crystals were obtained. Orange sheet-like crystals were selected by hand and washed with distilled water and ethanol (99.7%), respectively (Yield: 0.132 g, 23.0% based on Sn). EDS analysis gave the average Zn: Sn: Se molar ratio of 1.0: 3.0: 7.8, very close to that determined by the single-crystal diffraction. Anal. Calcd (%) for [(Me)2NH2]2ZnSn3Se8: C 4.19, H 1.41, N 2.44%; found: C 4.11, H 1.49, N 2.36%.


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Synthesis of [NH4]3AgSn3Se8 (2). 0.072 g (0.5 mmol) of freshly prepared AgCl, 0.154 g (1.3 mmol) of Sn, 0.316 g (4.0 mmol) of Se, 4.0 mL formamide and 1.0 mL hydrazine hydrate (80%) was combined and sealed in a 23 mL Teflon–lined stainless-steel autoclave at 160 °C for 6 days, and then cooled to room temperature. After isolation, a mixture of unidentified black powders and dark-red sheet-like crystals were obtained. Dark-red sheet-like crystals were selected by hand and washed with distilled water and ethanol (99.7%), respectively (Yield: 0.164 g, 32.9% based on Sn). EDS analysis gave the average Ag: Sn: Se molar ratio of 1.0: 2.8: 7.3, very close to that determined by the single-crystal diffraction. Anal. Calcd (%) for [NH4]3AgSn3Se8: H 1.05, N 3.65%; found: H 1.01, N 3.55%. Synthesis of [CH3NH3]2[H3O]Ag5Sn4Se12·C2H5OH (3). A mixture of freshly prepared AgCl (0.179 g, 1.25 mmol), Sn (0.118 g, 1.0 mmol), Se (0.237 g, 3.0 mmol) and methylamine (33−40% alcohol solution, 4.0 mL) was sealed in a 23 mL Teflon-lined stainless-steel autoclave. The resultant mixture was heated to 160 °C for 7 days and then cooled to ambient temperature naturally. The product consists of dark-red block-like crystals along with a large amount of darkred microcrystal powder. Dark-red block-like crystals of 3 were obtained by filtration, washed several times with ethanol (99.7%) and selected by hand (Yield: 0.060 g, 9.2% based on Sn). After filtration and isolation, the dark-red microcrystal powder was subsequently verified as compound 3 by PXRD, TGA and EA. EDS analysis gave the average Ag: Sn: Se molar ratio of 1.3: 1.0: 2.9, very close to that determined by the single crystal diffraction. Anal. Calcd (%) for [CH3NH3]2[H3O]Ag5Sn4Se12·C2H5OH: C 2.29, H 1.01, N 1.34%; found: C 2.10, H 1.03, N 1.44%. Synthesis of [CH3NH3]6Ag12Sn6S21 (4). The reagents including freshly prepared AgCl (0.143 g, 1.0 mmol), Sn (0.118 g, 1.0 mmol), S (0.128 g, 4.0 mmol) and methylamine (33−40% alcohol


6

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solution, 4.0 mL) were sealed in a 23 mL Teflon-lined stainless steel autoclave, heated at 140 °C for 8 days. Then the closed apparatus was taken out from the oven and cooled to room temperature naturally under ambient condition. After isolation, a mixture of unidentified black, orange and yellow powders, and red block-shaped crystals were obtained. Red block-shaped crystals of 4 were selected by hand, washed by distilled water and ethanol (99.7%), and then dried in air. The yield of the crystals of 4 is 0.034 g, 14.2% based on AgCl. EDS analysis gave the average Ag: Sn: S molar ratio of 1.9: 1.0: 3.2, very close to that determined by the single crystal diffraction. Anal. Calcd (%) for [CH3NH3]6Ag12Sn6S21: C 2.51, H 1.26, N 2.92%; found: C 2.62, H 1.24, N 2.88%. Crystal Structure Determination. Intensity data collections of compounds 1, 2 and 3− −4 were performed on an Xcalibur E Oxford diffractometer with graphite-monochromated MoKα radiation (λ = 0.71073 Å) at 293 K, a Rigaku MM007−CCD diffractometer with graphitemonochromated MoKα radiation (λ = 0.71073 Å) at 293K and a SuperNova Oxford diffractometer with graphite-monochromated MoKα radiation (λ = 0.71073 Å) at 100 K, respectively. The structures of compounds 1−4 were solved by direct methods and refined by full-matrix least-squares on F2 using the SHELX−2014 program package.55 For compound 1, the M’ site consisting of Zn(1) and Sn(1) atoms with 0.5/0.5 occupancy ratio was ultimately refined with common positional and displacement parameters (EXYZ and EADP commands, respectively); some constraints (DFIX, ISOR and SIMU) were applied to the C and N atoms to obtain the chemical–reasonable models and reasonable atomic displacement parameters. For compound 3, some constraints (DFIX, ISOR and SIMU) were applied to the [CH3NH3]+ and ethanol molecules. In compound 4, the Ag(8) and Ag(8B) atoms are disordered with the refined site occupancies of 0.44(3) and 0.56(3), and SIMU was applied to the Ag(8) and Ag(8B) atoms


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to obtain the reasonable atomic displacement parameters. Non-hydrogen atoms were refined with anisotropic displacement parameters and the hydrogen atoms attached to the C, N and O atoms are located at geometrically calculated positions. The empirical formulae were confirmed by the TGA and EA results. Detailed crystallographic data and structure-refinement parameters of compounds 1−4 are summarized in Table 1. Selected bond lengths, bond angles and hydrogen bonds data are listed in Tables S1−S8 in the Electronic Supporting Information (ESI). Electronic Structure Calculations. Single-crystal structural data of compound 4 was used for the theoretical calculation. The band structure as well as density of states (DOS) calculations for compound 4 based on the density functional theory (DFT) method was made by using the totalenergy code, CASTEP.56 The Perdew-Burke-Ernzerhof (PBE) functional of the generalized gradient approximations (GGA) was employed as the exchange-correlation functional.57,58 The valence atomic configurations were 1s2, 2s22p2, 2s22p3, 3s23p4, 4d105s1 and 5s25p2, for H, C, N, S, Ag and Sn, respectively. The number of plane waves included in the basis was determined by a cutoff energy of 400 eV, and the numerical integration of the Brillouin zone was performed using a 3 × 3 × 3 Monkhorst−Pack k-point. Photocatalytic Activity for Degradation of CV. The photocatalytic activity of compound 3 was evaluated by the degradation of CV under visible light irradiation of a 300 W Xe lamp equipped with a cutoff filter (λ > 420 nm). Reactions were performed in a quartz reaction vessel at ambient temperature. The distance between the Xe lamp and the reaction solution was ∼15 cm. In a typical photocatalytic experiment, 30 mg of photocatalyst was dispersed into 50 mL of 1 × 10−5 M CV solution. Before irradiation, the solution was initially magnetically stirred for 40 min in the dark to ensure adsorption–desorption equilibrium. After each 10 min intervals, 4 mL of CV solution was removed from the system for analysis. After 60 min of photoreaction, the


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suspension was centrifugalized at a speed of 9000 rpm/min for 5 min, and the resulting solution was analyzed on a SHIMADZU UV-2600 UV−vis spectrometer. Meanwhile, a blank experiment in the absence of the photocatalyst under visible light irradiation was also performed, and the corresponding CV solution was dealt with via the above-mentioned method.

RESULTS AND DISCUSSION Syntheses. In the syntheses of title compounds, we found that organic amine and the second agent (e.g. methanol, ethanol, and hydrazine) as mixed solvents have a beneficial effect on the crystallization of the desired products. While the absence of the second agent or using methylamine (33−40% aqueous solution) instead of methylamine (33−40% alcohol solution) yielded a failure to obtain the final products. To the best of our knowledge, this may be due to the dramatic changes of certain thermophysical properties of the solvent (e.g. pH, density, viscosity and diffusion coefficient), which are of great benefit to the diffusivity and solubility of reactants and crystal growth. By using this method, we recently synthesized a series of novel heterometallic chalcogenidometalates with the anionic architectures ranging from 1D chain/ribbon,

2D

layer,

to

[CH3NH3]20Ge10Sb28S72·7H2O,4

3D

network.4,24,49−52,59,60

Representative

examples

are

[(CH3CH2CH2)2NH2]3Ge3Sb5S15·0.5(C2H5OH),4

[NH3CH3]4[In4SbS9SH],50 and [PAH]3[In3Sb2S9] (PA = n-propylamine).52 In this paper, we further developed it in the syntheses of M−Sn−Q (M = Zn, Ag; Q = S, Se) compounds. In addition, we also found that reaction temperature has a large effect on the methylaminedirected Ag−Sn−S system. Compound 4 was synthesized in a manner analogous to that for compound [CH3NH3]2Ag4SnIV2SnIIS846 except that the reaction temperature was changed from 160

°C

for

compound

[CH3NH3]2Ag4SnIV2SnIIS8

to

140

°C.

Compared

to


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[CH3NH3]2Ag4SnIV2SnIIS8,46 compound 4 features a 3D open-framework structure of [Ag12Sn6S21]n6n− containing only the Sn(IV) atoms, the complex anionic framework of which contains three types of basic building blocks, namely, [AgS2] dumbbells, [AgS3] triangles and [AgS4] tetrahedra. Crystal Structure Descriptions. [(Me)2NH2]2ZnSn3Se8 (1). Single-crystal X-ray diffraction analyses revealed that compound 1 crystallizes in the noncentrosymmetric space group of C2 (No. 5) and features a 2D anionic layer of [ZnSn3Se8]n2n– that is built up by interconnections of [ZnSn3Se10] T2 clusters (Figure 1). The asymmetric unit of compound 1 contains half a formula unit, that is, one M’ site (M’ = 0.5Zn(1) + 0.5Sn(1), 4c), one Sn site (Sn(2), 4c), five Se sites (Se(1), Se(3) and Se(4) in 4c site, and Se(2) and Se(5) atoms in 2b site with 2 symmetry), and one dimethylamine cation. It is noteworthy that the M’ site consists of Zn(1) and Sn(1) atoms with 0.5/0.5 occupancy ratio, the coordination geometry of which can be described as a distorted [M’Se4] tetrahedron. Thus the molar ratio of Zn: Sn in compound 1 is 1: 3, which was further confirmed by EDS analysis (Figure S9, ESI). The M’−Se bond distances and Se–M’–Se angles fall in the range of 2.455(4)−2.503(4) Å and 97.59(15)–115.30(13)°, respectively (Table S1, ESI). Likewise, the Sn(2) atoms are also in a distorted tetrahedral environment, with Sn(2)–Se distances in the range of 2.502(4)–2.523(4) Å, and Se–Sn(2)–Se angles in the range of 104.53(15)–114.07(13)°, respectively (Table S1, ESI). Also noteworthy is that the Sn(2)–Se distances are slightly longer than those in [M’Se4] tetrahedra. These bond lengths and observed bond angles are normal and comparable with those in

compounds,

such

as

[AEPH2]Zn2Sn2Se7,34

[DBNH][Zn0.5Sn0.5Se2],32

[K10(H2O)16(MeOH)0.5][Zn4(µ4-Se)(SnSe4)4],61 and [(TEPA)Mn]4[Ga4Zn2Sn4Se20] (TEPA = tetraethylenepentamine).62


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As depicted in Figure 1a, two [SnSe4] and two [M’Se4] tetrahedra are interconnected via vertex-sharing to form a diamond-like [ZnSn3Se10] T2 cluster, which further links four adjacent clusters through sharing Se(3) atoms resulting in a 2D anionic layer of [ZnSn3Se8]n2n–. The windows that perforate the [ZnSn3Se8]n2n– layers are defined by the 16-membered rings formed by four [SnSe4] and four [M’Se4] tetrahedra with the dimensions of 7.78 ×7.78 Å2. Regarding the [ZnSn3Se10] T2 units as 4-connected nodes, the [ZnSn3Se8]n2n– anionic layers in compound 1 can be classified as a 4-connected topology with a point symbol of (44·62) (Figure S1, ESI). The charge-compensating dimethylamine cations reside in the interlayered spaces forming hydrogen bonds with the anionic layers (Figure 1b); the distances of N···Se in N–H···Se and C···Se in C– H···Se fall in the ranges of 3.48(15)–3.65(5) and 3.51(6)–3.7(2) Å (Table S2, ESI), respectively. Although the anionic layer of compound 1 has the same M: Sn ratio as those of compounds Cs2MSn3Se8 (M = Zn, Cd, Hg),63 their crystal structures are different. The latter compounds feature a 2D anionic layer of [MSn3Se8]n2n– characteristic of crown-like [MSn3Se11] units, while the anionic layer of compound 1 is built up by interconnections of [ZnSn3Se10] T2 clusters by vertex-sharing. Indeed, the anionic layers of compound 1 are closely related to those found in [H2dap]2Ga4Se8 (dap = 1,2-diaminopropane),64 KInS2,65 [NH4][InSe2],66 TlGaSe2,67 TlGaS268 and TlInS2,69 in which the adamantine-like [M4Q10] T2 cluster as SBUs was composed of four corner-linked [MQ4] tetrahedra. Hitherto, although several organically templated M−Sn−Q (M = Mn, Zn, Cd, Hg, Ga, In; Q = S, Se) compounds have been synthesized under mild solvothermal conditions,23,24,30−44,46 2D M−Sn−Q compounds based on T2 clusters as SBUs have rarely been isolated. Compound 1 represents a rare example of organically templated 2D M−Sn−Q compounds characteristic of T2 cluster as SBUs. Significantly, the first utilization of [(Me)2NH2]+ as templates and the Zn: Sn:


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Se molar ratio (1: 3: 8) of compound 1 are unique among those in the reported organically templated Zn–Sn–Se compounds. [NH4]3AgSn3Se8 (2). Compound 2 crystallizes in the tetragonal space group of P4/nbm (No. 125), and features an infinite linear anionic chains of [AgSn3Se8]n3n– (Figure 2). The asymmetric unit of compound 2 contains 1/8 of the formula unit, that is, one Ag site (Ag(1) in 2c site with 4ത 2m site symmetry), two Sn sites (Sn(1) in 4h site with 2.mm site symmetry, and Sn(2) in 2d site with 4ത 2m site symmetry), two Se sites (Se(1) and Se(2) in 8m site with mirror site symmetry) and two NH4+ ion (N(1) in 2a site with 422 site symmetry, and N(2) in 4g site with 4.. site symmetry). As shown in Figure 2a, edge-sharing of three tetrahedral [SnSe4] units produces linear [Sn3Se8]4– building blocks, which are further interconnected by Ag+ ions to form an infinite straight [AgSn3Se8]n3n– anionic chain. In the [AgSn3Se8]n3n– chain, all the Ag and Sn atoms are in a distorted tetrahedral coordination geometry with four Se atoms. The Ag(1)−Se and Sn(2)−Se bond distances amount to 2.7776(11) Å and 2.5283(9) Å, and the Se−Ag(1)−Se and Se−Sn(2)−Se angels fall in the range of 95.68(4)−116.78(2)° and 97.47(4)−115.79(2)°, respectively (Table S3, ESI). In the [Sn(1)Se4] tetrahedron, however, there exists two sets of Sn−Se bond lengths, 2.6199 (10) and 2.4871(10) Å. The Ag−Se and Sn−Se distances are normal and compare well with the values observed in two isostructural compounds A3AgSn3Se8 (A = K+, Rb+).70 All the Se2– ions act as bidentate metal linkers to bond one Ag and one Sn atoms or two Sn atoms. The infinite [AgSn3Se8]n3n– anionic chains propagate along the c axis and are well separated by charge balancing NH4+ cations (Figure 2b). The charge balancing NH4+ cations form extensive N−H···Se hydrogen bonds with Se atoms of the anionic chains; the distances of N−H···Se hydrogen bond distances and angles fall in the range of 3.431(3)−3.5763(11) Å and 105.8−166.6° (Table S4, ESI).


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[CH3NH3]2[H3O]Ag5Sn4Se12·C2H5OH (3). Compound 3 crystallizes in the tetragonal space group of P4ത 21m (No. 113), and it is isomorphic with [(Me)2NH2]0.75[Ag1.25SnSe3].24 Its structure features a 3D [Ag5Sn4Se12]n3n− anionic framework, containing intersecting 3D channels in which the charge balancing [CH3NH3]+ and [H3O]+ cations along with lattice ethanol molecules reside (Figure 3). The asymmetric unit of compound 3 consists of 1/4 of a formula unit, that is, two Ag sites (Ag(1) in 2b site with 4ത .. site symmetry, Ag(2) in 8f site), one Sn site (Sn(1) in 8f site), four Se sites (Se(1) and Se(3) in 8f site, Se(2) and Se(4) in 4e site with mirror site symmetry), 1/2 of one [CH3NH3]+, 1/4 of one [H3O]+ and 1/4 of one ethanol molecule. In the open framework of [Ag5Sn4Se12]n3n−, all the Sn4+ ions are four-coordinated. The Sn–Se bond lengths and Se–Sn–Se angles are normal and compare well with the values observed in [(Me)2NH2]0.75[Ag1.25SnSe3].24 The Ag(1) atoms are surrounded by four Se atoms to form a regular tetrahedron, while the Ag(2) atoms adopt a trigonal planar coordination geometry. The Ag−Se bond distances and observed Se−Ag−Se angles are also normal and call for no further comments.24 Vertex-sharing of four neighboring trigonal planar [Ag(2)Se3] units produce unusual [Ag(2)4Se8] clusters (Figure S3, ESI), which are further connected by Ag(1)+ ions via its four terminal Se(1) atoms to form the infinite straight [Ag5Se8]n11n− chain extended along the c axis (Figure 3a). The Ag(2)−Ag(2) separations scatter from 3.0969(13) to 3.2063(15) Å (Table S5, ESI). Each [Ag5Se8]n11n− chain further connects four adjacent [Ag5Se8]n11n− chains via four arrays of [Sn2Se6] units (Figure 3b) by sharing their Se(1) and Se(3) atoms, giving rise to a 3D [Ag5Sn4Se12]n3n− anionic framework (Figure 3c), wherein the [Sn2Se6] dimers are composed of two [SnSe4] tetrahedra by edge-sharing. It was also noted that compound 3 contains intersecting 3D channels along the c axis (Figure 3c) and [1 1 0]/[1 −1 0] directions (Figure S4a, ESI), wherein the [1 1 0] and [1 −1 0] directions


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are equivalent. The channels parallel to the c axis are petal-shaped with a cross section of 7.74 × 7.27 Å2 (Figure 3d), the sizes of which are slightly larger than those found in [(Me)2NH2]0.75[Ag1.25SnSe3] (7.62 × 7.14 Å2).24 Whereas the sizes of the channels running along the [1 1 0]/[1 −1 0] directions in compound 3 and [(Me)2NH2]0.75[Ag1.25SnSe3]24 vary from 6.38 × 6.34 Å2 to 5.84 × 7.10 Å2 (Figure S4b, ESI). The structure differences between two compounds may be attributed to the different templates used in the syntheses and framework flexibility of chalcogenidometalates. The large 24-membered ring window of the channels running along the c axis is constructed from four [Sn(1)2Se6] dimers and four trigonal planar [Ag(2)Se3] units by corner-sharing, Figure 3d. While along the [1 1 0]/[1 −1 0] directions, the opening of the 16-membered ring channel is delimited by two [Sn(1)2Se6] dimers, two trigonal planar [Ag(2)Se3] units and two [Ag(1)Se4] tetrahedra by vertex-sharing (Figure S4b, ESI). The protonated [CH3NH3]+ and [H3O]+ cations as SAAs and CBAs along with lattice ethanol molecules residing in the channels form extensive N−H···Se and C−H···Se hydrogen bonds with Se atoms of the anionic network. The N−H···Se and C−H···Se hydrogen bond distances and angles fall in the range of 3.436(14)−3.451(8) Å and 160(11)−162(17)°, 3.37(7)−3.65(6) Å and 121.9−157.7° (Table S6, ESI), respectively, implying the weak N−H···Se and C−H···Se hydrogen bonding interactions. Exluding all the guest molecules and cations in the channels, the effective solvent accessible volume occupies 31.3% of the total cell volume calculated by using the PLATON program.71 [CH3NH3]6Ag12Sn6S21 (4). Single crystal X-ray diffraction analyses revealed that compound 4 adopts the monoclinic space group of P21/c (No. 14) and features an unprecedented 3D openframework anionic structure of [Ag12Sn6S21]n6n–, Figure 4. The asymmetric unit of compound 4 contains one formula unit. In the framework of [Ag12Sn6S21]n6n–, all the Sn atoms are


14

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tetrahedrally coordinated by sulfur atoms with Sn−S bond lengths and S−Sn−S bond angles ranging from 2.3456(14) to 2.4660(14) Å and 102.71(4) to 120.87(5)° (Table S7, ESI), respectively. Interestingly, the Ag+ ions adopt three different coordination modes, i.e. Ag(3), Ag(6), Ag(7), Ag(8) and Ag(11) feature trigonal planar coordination geometries; Ag(1), Ag(2), Ag(4), Ag(5), Ag(10) and Ag(12) atoms are tetrahedrally surrounded by four S atoms; while the Ag(9) atom adopts a linear coordination geometry (Figure S5, ESI). The bond lengths of Ag−S and bond angles of S−Ag−S in trigonal planar [AgS3] units lie in the normal ranges of 2.4239(14)−2.7487(14) Å and 99.90(4)−150.70(4)° (Table S7, ESI), respectively, which compare well with those found in related compounds such as [1,4-dabH2]Ag2SnS4 (1,4-dab = 1,4-diaminobutane),36 [enH2]Ag2SnS4,35 K4Ag2Sn3S9·2KOH,72 and A2Ag6Sn3S10 (A = K+, NH4+).47,73 The Ag−S bond distances and observed S−Ag−S bond angles in other two coordination geometries are also normal calling for no further comments.35,36,46,47,72−75 One [Ag(9)S2] dumbbell, one [Ag(11)S3] triangle and two [AgS4] tetrahedra (i.e. [Ag(1)S4] and [Ag(4)S4]) are condensed by corner- or edge-sharing to form a unique [Ag4S8] cluster, denoted as C1 (Figure 4a). Whereas three trigonal planar [AgS3] units (i.e. [Ag(3)S3], [Ag(6)S3] and [Ag(7)S3]) and one [Ag(2)S4] tetrahedron are jointed together via corner- or edge-sharing to produce another unique [Ag4S8] cluster, denoted as C2 (Figure 4b). Such two [Ag4S8] clusters are interconnected by sharing S(7) and S(3) atoms to form a [Ag8S14] moiety. As shown in Figure 4c, there exists a [Ag3S8] moiety with a 6-membered [Ag3S3] ring defined by one trigonal planar [AgS3] unit and two [AgS4] tetrahedra via vertex-sharing. The [Ag8S14] and [Ag3S8] moieties are interconnected via corner-sharing S(11) and S(16) atoms to constitute one [Ag11S20] moiety, which further connects two adjacent such [Ag11S20] moieties through sharing S(19) atoms to form a [Ag11S19]n27n− ribbon (Figure S6, ESI). Such two centrosymmetric [Ag11S19]n27n−


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ribbons are interconnected by the tetrahedral Ag(10) atoms to form a [Ag12S19]n26n− double ribbon (Figures 4d and 4e), which further links four neighboring identical ones via sharing S(21) atoms to form a 3D [Ag12S17]n22n− anionic framework (Figure S7, ESI). Then the [Sn2S7] dimers (Figure 4f) are decorated in the above mentioned 3D [Ag12S17]n22n− anionic framework by corner-sharing S atoms to result in a more complex 3D open anionic framework of [Ag12Sn6S21]n6n− with 1D channels (Figure 4g). The channels parallel to the a axis are distorted cross-shaped with a cross section of 6.40 × 10.13 Å2, which are composed of a 20-membered ring defined by two [AgS3], two [AgS4] and six [SnS4] units via corner-sharing (Figure S8, ESI). The protonated methylamine cations as SAAs and CBAs residing in the channels form extensive N−H···S and C−H···S hydrogen bonds with S atoms of the anionic network. The N−H···S and C−H···S hydrogen bond distances and angles fall in the range of 3.223(5)−3.629(5) Å and 113.0−174.7°, 3.594(6)−3.748(5) Å and 119.6−145.1° (Table S8, ESI), respectively, implying the weak N−H···S and C−H···S hydrogen bonding interactions. In addition, our experiments proved that compounds 1, 2 and 4 showed no ion-exchange property. Whereas the organic amine cations in compound 3 can be readily exchanged by Cs+ and Rb+, and other alkali ions (K+, Na+) and alkaline earth ions (Ba2+, Sr2+, Ca2+, Mg2+) could not be exchanged at all (Figure S10, ESI). To the best of our knowledge, the supreme selectivity of compound 3 for specific ions such as Cs+ and Rb+ may be mainly ascribed to its soft basic framework structure with channels of particular size and shape.2,4,24,50 The solvent-volume in compound 4 excluding the organic cations is about 27.1% calculated by PLATON.71 Among the transition metal ions (Mn2+, Fe2+, Co2+, Ni2+, Cu+, Ag+, Zn2+, Cd2+, and Hg2+), thiophilic group 11 metal ion Ag+ is a remarkable candidate, appearing to be more readily to be incorporated into the [SnxQy]n− units to construct novel heterometallic anionic framework due to


16

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the flexible coordination behavior of Ag+ to chalcogen Q2− (Q = S, Se, Te). It has been found that Ag+ ion can adopt various coordination environments like [AgQ2] dumbbell, [AgQ3] triangle or [AgQ4] tetrahedron in the Ag−Sn−Q compounds such as 0D-[Hen]4[Ln(en)4]2[Ag6Sn6S20]·3en (Ln = Er, Tm and Yb),76 1D-[1,4-dabH2]Ag2SnS4,36 1D-A3AgSn3Se8 (A = K+, Rb+),70 1DK2Ag2Sn2Se6,77 2D-[enH2]Ag2SnS4,35 2D-K4Ag2Sn3S9·2KOH,72 2D-K4Ag2Sn3S9·2H2O,74 2DK2Ag2SnSe4,78 2D-[Bmmim]7[AgSn12Se28] (Bmmim = 1-butyl-2,3-dimethyl-imidazolium),79 2D-[Mn(en)3][Ag6Sn2Te8],80 3D-[CH3NH3]2Ag4SnIV2SnIIS8,46 3D-A2Ag6Sn3S10 (A = K+, NH4+),47,73

3D-BaAg2SnQ4

(Q

=

S,

Se),81,82

3D-[NH4]4Ag12Sn7Se22,48

3D-

[(Me)2NH2]0.75Ag1.25SnSe3,24 3D-[M(NH3)6][Ag4Zn4Sn3Se13] (M = Zn, Mn),83 and 3DK2Ag2SnTe4.84 However, the existing examples normally feature simple [AgxQy]n− moieties, which are constructed by only one or two types of [AgQx] ( x = 2, 3, 4) basic building blocks. Compound 4 represents a rare organically templated 3D Ag−Sn−Q compound with a complex [Ag12Sn6S21]n6n− anionic framework. More importantly, it represents the first 3D Ag−Sn−S compound based on the combination of three types of basic building blocks of [AgS2] dumbbells, [AgS3] triangles and [AgS4] tetrahedra. Thermal Analyses. The thermal stabilities of compounds 1−4 were examined by TGA under a flow of nitrogen (Figure 5). The TGA curves revealed that compound 1 displays a weight loss of 14.8% (calcd. 14.9%) in the range of 250−400 °C, corresponding to the loss of two (Me)2NH and one H2Se molecule per formula. Compound 2 loses three NH3 and three halves H2Se molecules per formula in the range of 200−515 °C with a total weight loss of 14.9%, which is close to the calculated amount (15.0%). With increasing the temperatures, the progressive weight loss continued and still did not achieve the balance at 800 °C. Compound 3 features a three-step weight loss in range of 30−250 °C. The initial weight loss of 1.8% below 100 °C corresponds to


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removal of ethanol molecules (calcd. 2.2%). The weight loss between 100 and 155 °C is attributed to removal of 1/4 of one H2O and 1/8 of one H2Se molecule per formula with an observed total weight loss of 2.9%, which is close to the theoretical value of 2.8%. In the range of 155−250 °C, 1/2 of one CH3NH2 and 1/4 of one H2Se molecule per formula are further removed with an observed total weight loss of 7.7%, in accordance with the theoretical value of 6.9%. Compound 4 begins to lose weight at about 200 °C, and it has a final weight loss of 10.0% (calcd. 10.0%) when the temperature reaches 300 °C. The observed weight loss can be attributed to the removal of six CH3NH2 and three H2S molecules per formula. Optical Properties. The solid-state optical diffuse reflection spectra of the title compounds 1−4 were measured on powder samples at room temperature. As shown in Figure 6, the absorption edges are 2.00 eV for 1, 1.82 eV for 2, 1.80 eV for 3, 2.06 eV for 4, respectively. The band gap of compound 1 was close to that of [AEPH2]Zn2Sn2Se7 (2.30 eV).34 The band gaps of compounds 2 and 3 were close to those of other silver-selenidostannate, such as K2Ag2SnSe4 (1.80 eV),78 Rb3AgSn3Se8 (1.80 eV),70 [(Me)2NH2]0.75[Ag1.25SnSe3] (1.85 eV).24 Likewise, the band gap energy of compound 4 is comparable to that of the reported silver-thiostannate, such as [enH2]Ag2SnS4 (2.20 eV),35 [CH3NH3]2Ag4SnIV2SnIIS8 (2.10 eV),46 K4Ag2Sn3S9·2H2O (2.40 eV),74 and K2Ag6Sn3S10 (1.80 eV).73 Theoretical Studies. To gain further insight into the electronic structure of the title compounds, compound 4 was selected as the representative to calculate their band structures, density of states (DOS) as well as partial density of states (PDOS). It is found that compound 4 has an indirect band gap of about 1.18 eV (Figure S13, ESI), which is smaller than the experimental value of 2.06 eV deduced from the solid state UV-visible absorption. As is wellknown, such a discrepancy between the experimental and calculated band gap is due to the


18

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inaccurate description of eigenvalues of the electronic states by GGA,57,58 which often causes quantitative underestimation of the band gaps for semiconductors and insulators.85−87 In the DOS and PDOS curve (Figure 7), the valence bands (VBs) just below the Fermi level (the Fermi level is set at 0 eV) is mainly made up of S−3p, Ag−4d and C−2p states, whereas the conduction bands (CBs) above the Fermi level from 1.1 to 2.6 eV is mainly dominated by C−2p, S−3p, C−2s and Sn−5s states. The region between 2.6 and 4.5 eV is mainly derived from C−2p and C−2s states. Photocatalytic Activity. The narrow band gap and high aqueous stability of compound 3 encourages us to investigate its photocatalytic activity (Figure S12a, ESI), which was evaluated by degradation of CV as the test pollutant under visible light irradiation. The characteristic absorption of CV at about 589 nm was selected for monitoring the adsorption and photocatalytic degradation process. The degradation efficiency is defined as C/C0, where C and C0 represent the remnant and initial concentration of the organic dye. As shown in Figure 8, the photolysis of CV without the photocatalyst could be neglected. Satisfyingly, the degradation ratio of CV reached 96 % when exposed to visible light irradiation for 10 min, and achieved nearly 100 % after 60 min, resulting in complete decolorization. This is in stark contrast with the lengthy degradation time required for other metal chalcogenide photocatalysts, such as [CH3NH3]2Ag4SnIV2SnIIS8,46 [CH3NH3]20Ge10Sb28S72·7H2O,4 [(CH3)2NH2]2In2Sb2S751 and [Ni(1,2-dap)3]HgSb2S5 (1,2-dap = 1,2-propylenediamine),88 which normally ranges from 4 h to as much as 10 h. The degradation efficiency of 3 was also significantly higher than those of some well-known materials (e.g., Ndotted P25),89 and comparable with some metal halide photocatalysts.89−92 For example, the CV photodecolorization over N-dotted P25 was negligible.89 While some metal halide photocatalysts displayed almost entirely photocatalytic degradation for CV when exposed to visible light irradiation for 10 min; representative examples are [Cu(2,2-bipy)2I]2Cu7I9,90 K[Mn(2,2-


19


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bipy)3]2Cu6I11,90 [Ni(phen)3]2Cu6I10 (phen = 1,10-phenanthroline)91 and [(Ni(2,2-bipy)3][H-2,2bipy]Ag3I6).89 XRD characterization shows that there is no obvious change before and after the photocatalytic process, demonstrating the stability of compound 1 as the catalyst (Figure S12b, ESI). We attribute the high photocatalytic efficiency and high stability to suitable energy band gap corresponding to absorption of visible light compared to various oxide semiconductor materials, coupled with high stability of skeleton structure of metal chalcogenides. CONCLUSIONS. In summary, four new small-amine-molecule-directed M−Sn−Q compounds (M = Zn, Ag; Q = S, Se) have been solvothermally synthesized and structurally, optically, and thermally characterized. Compound 1 represents a rare organically templated 2D Zn−Sn−Se compound characteristic of [ZnSn3Se10] T2 cluster as SBUs. Compound 2 features a straight 1D [AgSn3Se8]n3n– anionic chain. Compound 3 exhibits a 3D open [Ag5Sn4Se12]n3n– anionic framework with intersecting 3D channels. Compound 4 possesses a complex 3D [Ag12Sn6S21]n6n− anionic framework, which represents the first 3D Ag−Sn−Q compound based on the combination of three types of basic building blocks of [AgS2] dumbbells, [AgS3] triangles and [AgS4] tetrahedra. Interestingly, compound 3 exhibited the ability of photocatalytic degradation of CV under visible light irradiation. Future studies will be focused on the exploratory synthesis of more M−Sn−Q functional compounds and deep understanding of relationship of structure and property.


20

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FIGURES

Figure 1. (a) Polyhedral view of the [ZnSn3Se8]n2n– anionic layer. (b) A packing view of compound 1 along the [1 1 0] direction.


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Page 22 of 44

Figure 2. (a) View of the [AgSn3Se8]n3n– anionic chain extended along the c axis. (b) Perspective view of the structure of compound 2 along the c axis. H atoms are omitted for clarity.

Figure 3. (a) View of the [Ag5Se8]n11n− chain extended along the c axis. (b) The [Sn2Se6] unit. (c) Perspective view of the structure of compound 3 along the c axis. (d) View of the 24-membered ring window of the channel in compound 3 along the c axis. C, N, O and H atoms are omitted for clarity.


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Figure 4. Crystal structure of 4. (a) The [Ag4S8] cluster C1. (b) Another unique [Ag4S8] cluster C2. (c) The [Ag3S8] unit containing a 6-membered [Ag3S3] ring. (d) The [Ag12S19]n26n− doubleribbon extending along the a axis. (e) The [Ag12S19]n26n− double ribbon viewed along the a axis. (f) The [Sn2S7] unit. (g) Perspective view of the anionic framework along the a axis. C, N and H atoms are omitted for clarity.


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Page 24 of 44

Figure 5. Thermogravimetric curves for compounds 1−4.

Figure 6. Solid-state optical absorption spectra of compounds 1− −4.

Figure 7. Total density of states and partial density of states for compound 4. The Fermi level is set at 0 eV (dotted line).


24

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Figure 8. Photodegradation of CV by compound 3 monitored as the normalized change in concentration as a function of irradiation time.


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Page 26 of 44

Table 1. Crystallographic data and structural refinement details for compounds 1–4.

compounds

1

2

3

4

empirical formula

C4H16N2Se8Sn3Zn

H12AgN3Se8Sn3

C4H21Ag5N2O2Se12Sn4

C6H36Ag12N6S21Sn6

formula weight

1145.31

1149.75

2090.86

2872.25

crystal system

monoclinic

tetragonal

tetragonal

monoclinic

space group

C2

P4/nbm

P4ത 21m

P21/c

a/Ǻ

10.9607(12)

8.276(3)

13.6350(5)

18.8646(5)

b/Ǻ

11.0559(10)

8.276(3)

13.6350(5)

19.9115(6)

c/Ǻ

9.6829(15)

13.461(7)

9.1491(5)

14.3125(4)

α/º

90.00

90.00

90.00

90.00

β/º

105.170(13)

90.00

90.00

100.117(3)

γ/º

90.00

90.00

90.00

90.00

V/Å3

1132.5(2)

922.0(8)

1700.93(15)

5292.5(3)

Z

2

2

2

4

T/K

293(2)

293(2)

100(2)

100(2)

ρcalcd /g cm-3

3.359

4.141

4.082

3.605

µ/mm-1

17.160

20.832

18.545

7.948

F(000)

1012

1004

1836

5256

Measured refls.

2311

6630

5169

31410

Independent refls.

1688

586

1877

11668

No. of parameters

111

26

133

482

Rint

0.0507

0.0305

0.0337

0.0366

GOF

1.025

1.000

1.008

1.005

a

0.0674

0.0259

0.0243

0.0292

0.1542

0.0744

0.0522

0.0503

R1 (I > 2σ(I))

b

wR(F2) (I > 2σ (I))

[a] R1 = ∑║Fo│–│Fc║/∑│Fo│. [b] wR2 = [ ∑w(Fo2−Fc2)2/∑w(Fo2)2]1/2.


26

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ASSOCIATED CONTENT Supporting Information. More structural details and figures, powder X-ray diffraction patterns, EDS and DFT calculation results. This material is available free of charge via the Internet at http://pubs.acs.org. Accession Codes. CCDC 1511781−1511784 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. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Fax: (+86)591–63173145. Notes The authors declare no competing financial interest. ACKNOWLEDGEMENTS This work was supported by the NNSF of China (Nos. 21521061 and 21373223) and 973 program (No. 2014CB845603). We acknowledge the Supercomputing Center of CNIC for providing the computer resources.

REFERENCES


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For Table of Contents Use Only

Presented here are the solvothermal syntheses and characterizations of four new small-aminemolecule-directed M−Sn−Q (M = Zn, Ag; Q = S, Se) compounds.


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Syntheses, Crystal Structures, and Optical and Photocatalytic

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