Cd3(MoO4)(TeO3)2: A Polar 3D Compound ... - ACS Publications

Nov 9, 2016 - (7) Lee et al. obtained the novel NCS compound Ga2Zn(TeO3)4 containing both d10 Zn2+ cations and SCALP Te4+ cations.(43) Kong et al...
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Cd3(MoO4)(TeO3)2: A Polar 3D Compound Containing d10−d0 SCALPEffect Cations Yuquan Feng,* Huitao Fan, Zhiguo Zhong, Hongwei Wang, and Dongfang Qiu* College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473061, China S Supporting Information *

ABSTRACT: The new polar 3D cadmium molybdotellurite Cd3(MoO4)(TeO3)2 was obtained by means of a hightemperature solid-state method. Cd3(MoO4)(TeO3)2 is a monoclinic crystal system, and it exhibits the polar space group P21 (No. 4). The structure of Cd3(MoO4)(TeO3)2 can be viewed as a complicated 3D architecture that is composed of distorted CdOn (n = 6, 7) polyhedra, TeO3 trigonal pyramids, and MoO4 polyhedra. The compound features the first 3D NCS cadmium molybdotellurite with 1D 4- and 6-MR channels and a polar structure originating from the TeO3 groups, MoO4 groups, and displacements of d10 Cd2+ cations. The results were further confirmed by calculations of the net polarization. The UV−vis spectrum and thermal properties indicate that Cd3(MoO4)(TeO3)2 exhibits a broad transparent region and excellent thermal stability. SHG tests of Cd3(MoO4)(TeO3)2 revealed that its response is approximately the same as that of KH2PO4 at the same grain size between 105 and 150 μm and that it is phase-matchable. materials Se2(B2O7) containing SCALP-effect Se4+ cations44 and Cd4BiO(BO3)3 containing BiO6 and CdOn (n = 6, 7) distorted polyhedra and planar BO33− groups.8 Sun and coworkers prepared the new NLO crystal Cs2GeB4O9 with planar BO33− groups.45 Mao and co-workers prepared the polar metal iodate Zn2(VO4)(IO3) with both d0 (V5+) and d10 (Zn2+) cations.5 These examples indicate that the exploration of new NLO crystal materials with a variety of NCS components should be a promising research field. The incorporation of cadmium is favorable for the formation of new NCS molybdotellurites with novel structural features and NLO properties. First, the d10 Cd2+ cation tends to exhibit asymmetric coordination environments for building NCS crystal materials. Second, the flexible coordination behavior of Cd2+ (CdO6 and CdO7) can enhance the NLO properties. In addition, either tetrahedral or octahedral coordination behavior of Mo6+ and trigonal-pyramidal TeO3 groups provide greater opportunities for the rational design of new polar oxides. Therefore, it is expected that the CdO−MoO3−TeO2 system, which combines Cd2+, Mo6+, and Te4+ cations, could generate new NLO crystal materials with outstanding optical properties. Moreover, to date, no NLO crystal material based on the CdO−MoO3−TeO2 system containing three types of potential chromophores (polar displacement d10 Cd2+ cation, SOJTdistorted d0 Mo6+ cation, and SCALP-effect Te4+ cation) has been reported in the series of metal tellurites. Based on this

1. INTRODUCTION Currently, second-order nonlinear optical (NLO) crystal materials are receiving increasing interest because of their diverse practical applications in the fields of frequency-doubling lasers, holographic storage, and so on.1−4 The variety of applications have given rise to significant efforts toward the discovery of new second-order NLO crystal materials.5 To date, many NLO crystal materials with enhanced UV transparency and excellent nonlinearity have been widely applied in industrial production, including β-BaB2O4 (BBO), LiB3O5 (LBO), CsB3O5 (CBO), and KTiOPO4 (KTP).6,7 A promising strategy for the synthesis of such materials is to use asymmetric components as building blocks, mainly including planar BO3 groups, second-order Jahn−Teller (SOJT) distorted d0 cations (Ti4+, V5+, Nb5+, and Mo6+), d10 cations (Zn2+ and Cd2+), and stereochemically active lone-pair (SCALP) effect cations (Se4+, Te4+, and I5+).8−38 The combination of multiple asymmetric components into the same compound might be favorable for noncentrosymmetric (NCS) crystal materials with large SHG effects. For example, Halasyamani and co-workers reported a series of new polar oxides containing Se4+ or Te4+/6+ cations: Zn2(MoO4) (AO3) (A = Se4+ or Te4+),39 Li6(Mo2O5)3(SeO3)6,40 and Pb3Mg3TeP2O14.41 Pan and coworkers prepared some new metal borates/borophosphates with planar BO3 groups or d10 cations (Zn2+ and Cd2+): K3B6O10Cl,3 Ba4B11O20F,11 Cs3Zn6B9O21,42 and Na3Cd3B(PO4)4.7 Lee et al. obtained the novel NCS compound Ga2Zn(TeO3)4 containing both d10 Zn2+ cations and SCALP Te4+ cations.43 Kong et al. reported novel NLO crystal © 2016 American Chemical Society

Received: September 7, 2016 Published: November 9, 2016 11987

DOI: 10.1021/acs.inorgchem.6b02117 Inorg. Chem. 2016, 55, 11987−11992

Article

Inorganic Chemistry consideration, in this article, we describe the synthesis, structure, thermal stability, UV−vis spectrum, and NLO properties of the novel cadmium molybdotellurite Cd3(MoO4)(TeO3)2. This compound not only features the first 3D NCS cadmium molybdotellurite with a polar structure, but also exhibits a wide UV-transparent region, good SHG effects, and high thermal stability.

Table 1. Crystallographic Data and Structure Refinement for Cd3(MoO4)(TeO3)2 formula fw temp (K) wavelength (Å) cryst syst space group a (Å) b (Å) c (Å) β (deg) vo l(Å3) Z density (g·cm−1) abs coeff (mm−1) F(000) limiting indices reflns collected/unique GOF on F2 R1, wR2 (I > 2σ) R1, wR2 (all data)

2. EXPERIMENTAL SECTION 2.1. Materials and Methods. All reagents used in the process of synthesis were purchased commercially. The results of energydispersive spectroscopy (EDS) were recorded on an FEI-Quanta 200 scanning electron microscope. Powder X-ray diffraction (PXRD) analysis of Cd3(MoO4)(TeO3)2 was performed on a Bruker D8advance instrument (Cu Kα, λ = 1.5418 Å). IR spectra were measured on a Perkin-Elmer FTIR spectrometer between 400 and 2000 cm−1. The UV−vis diffuse-reflectance spectrum of Cd3(MoO4)(TeO3)2 was measured on a PE Lambda 650 UV−visible spectrometer in the range of 200−850 nm at room temperature, using BaSO4 plate as the standard material (100% reflectance). The TG curve was measured under a N2 atmosphere on a STA-449-F3 Jupiter instrument at a heating rate of 10 °C·min −1 between 30 and 1400 °C. The SHG tests were performed by the Kurtz−Perry method under 1064-nm radiation. The samples of Cd3(MoO4)(TeO3)2 were sieved into five grain sizes as follows: 55−88, 88−105, 105−150, 150−200, and 200−250 μm. The KH2PO4 (KDP) powders of the same grain size ranges were used as references. 2.2. Synthesis of Cd 3 (MoO 4)(TeO 3) 2 . Single crystals of Cd3(MoO4)(TeO3)2 were obtained through a high-temperature solid-state reaction employing a mixture of high-purity reagents. A stoichiometric mixture of CdO (3 N, 0.2568 g), (NH4)6Mo7O24·4H2O (3 N, 0.6179 g), and TeO2 (3 N, 0.4788 g) in a molar ratio of 4:1:6 was ground carefully and packed into an alumina crucible, which was then capped with a cover. The alumina crucible was placed into a furnace and heated to 1073 K at a rate of 30 K·h−1. After being held at that temperature for 96 h, the sample was then cooled to 823 K at a rate of 5 K·h −1 and further held at this temperature for 24 h. Then, it was cooled to room temperature at a rate of 10 K·h−1. A mixture of colorless block single crystals Cd3(MoO4)(TeO3)2 in a ca. 43% yield (based on Cd) and white powder was obtained. The colorless crystals Cd3(MoO4)(TeO3)2 were picked out manually for structure determination and further investigations. Based on the results of structural analysis, the pure white powder phase of Cd3(MoO4)(TeO3)2 was prepared quantitatively by reacting a mixture of CdO, (NH4)6Mo7O24·4H2O, and TeO2 in a molar ratio of 21:1:14 (or CdO/ MoO3/TeO2 in a molar ratio of 3:1:2). The mixture was heated to 1053 K at a rate of 30 K·h−1 and kept at this temperature for 48 h. Then, the furnace was switched off, and the mixture was cooled to room temperature. The phase purity of the obtained Cd3(MoO4)(TeO3)2 powder was further confirmed by powder XRD pattern (Figure S2). 2.3. X-ray Crystallography. The data for the crystal (0.26 mm × 0.20 mm × 0.16 mm) were recorded on a Bruker APEX-II CCD diffractometer with Mo Kα radiation [λ = 0.71073 Å, T = 296(2) K]. The total number of collected reflections was 3997, and the number of unique reflections was 1646 (Rint = 0.0477). SADABS46 was utilized in the absorption correction of the crystal data. The direct method was applied to solve the structure, and SHELXL-97 software47 was employed to refine the structure by the full-matrix least-squares method on F2. All Cd, Te, Mo, and O atoms of this structure were refined anisotropically. The crystallographic data and structure refinement results for Cd3(MoO4)(TeO3)2 are reported in Table 1, and selected Te−O, Mo−O, and Cd−O distances are listed in Table S1.

Cd3(MoO4)(TeO3)2 848.34 296(2) 0.71073 monoclinic P21 (No. 4) 8.5165(16) 5.4850(10) 10.916(2) 108.4850(10) 483.62(15) 2 5.826 13.724 740 −10 ≤ h ≤ 10, −6 ≤ k ≤ 6, −12 ≤ l ≤ 12 3997/1646 (Rint = 0.0477) 1.026 R1 = 0.0466, wR2 = 0.1363 R1 = 0.0471, wR2 = 0.1367

and is in the polar space group P21 (No. 4). The asymmetric unit of Cd3(MoO4)(TeO3)2 contains two crystallographically unique Te sites, one unique Mo site, three unique Cd sites, and 10 unique O sites. Figure 1 shows the coordination

Figure 1. Coordination environments for the Te, Mo, and Cd sites.

environment for the Te, Mo, and Cd sites. Within the asymmetric unit, both Te1 and Te2 atoms are 3-foldcoordinated by three O atoms to form TeO3 trigonal pyramids. The Te−O bond lengths in the trigonal-pyramidal TeO3 group vary from 1.829(14) to 1.896(14) Å. Local asymmetric coordination environments presented in the Te4+ cations are assigned to the stereoactive lone pairs. The Mo1 atom adopts tetrahedral coordination with Mo−O bond lengths between 1.758(15) and 1.802(15) Å. The coordination modes of the three Cd atoms can be divided into two types, namely, sixcoordinated (Cd1 and Cd3) and seven-coordinated (Cd2) configurations. Both Cd1 and Cd3 atoms are six-coordinated with Cd−O distances varying from 2.076(15) to 2.8308(17) Å. The Cd2 atom is surrounded by seven O atoms with Cd−O bond lengths between 2.275(14) and 2.7687(18) Å. The Te− O, Mo−O, and Cd−O distances are comparable to those of previously reported compounds.39,44 Within the asymmetric unit, one trigonal-pyramidal Te2O3 group, one Cd3O 6 octahedron, and one Cd2O7 polyhedron are linked through vertex sharing to form a {Cd2TeO12} three-membered-ring (3MR) fragment, on either side of which are located a Te1O3

3. RESULTS AND DISCUSSION 3.1. Crystal Structure. Single-crystal structural analysis indicated that Cd3(MoO4)(TeO3)2 is monoclinic crystal system 11988

DOI: 10.1021/acs.inorgchem.6b02117 Inorg. Chem. 2016, 55, 11987−11992

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Inorganic Chemistry group and a {Mo1Cd1O9} fragment. The results of bond valence sum (BVS) calculations48 revealed that all Cd, Te, and Mo atoms display their normal oxidation states of 2+, 4+, and 6+, respectively, as confirmed by the calculated BVS values of 2.190, 1.867, 2.069, 3.988, 4.080, and 5.705 for Cd1, Cd2, Cd3, Te1, Te2, and Mo1, respectively (see Table S1). Cd3(MoO4)(TeO3)2 is thus a new polar oxide material, and its structure can be regarded as a complicated 3D architecture that contains distorted CdO6 octahedra, CdO7 polyhedra, TeO3 trigonal pyramids, and MoO4 polyhedra. Each Te1 atom is linked to the adjacent two CdO6 octahedra and three CdO7 polyhedra by one μ4-O and two μ3-O atoms, and each Te2 atom is bonded to the surrounding four CdO6 octahedra and one CdO7 polyhedron by three μ3-O atoms; that is, these TeO3, CdO6, and CdO7 ployhedra are further connected through shared corners or edges, extending into a 2D anionic layer of the form {Cd3Te2O10}∞6n− that is arranged in such way that each CdOn (n = 6 or 7) polyhedron is surrounded by four trigonal-pyramidal TeO3 groups and each TeO3 group is connected to five CdOn (n = 6 or 7) polyhedra (Figure 2). The

Figure 4. View of the crystal structure of the 3D architecture.

Moreover, it is worth pointing out that the 3D architecture exhibits one type of 1D 4-MR channel and two types of 1D 6MR channels along the b axis. The diameters of the 4-MR channels are about 3.392 Å × 4.156 Å, and those of the 6-MR channels are about 6.504 Å × 6.599 and 6.621 Å × 6.832 Å (Figure 5). The 4-MR channels are constructed by one CdO7

Figure 2. Crystal structure of the 2D anionic layer {Cd3Te2O10}∞6n− along the a axis.

Cd−O−Te bond angles fall in the range of 98.2(6)− 150.7(11)°. The {Cd3Te2O10}∞6n− anionic layers are linked with Mo6+ cations by the shared corners (Figure 3), leading to the new 3D structural architecture shown in Figure 4. Each MoO4 octahedron is surrounded by four O atoms belonging to three CdOn (n = 6 or 7) polyhedra. The Cd−O−Mo angles observed in the structure vary from 128.1(7)° to 137.1(7)°.

Figure 5. View of the 4-MR channel (red) and two types of 6-MR channels (yellow) along the b axis. MoO4, blue; CdOn, bright green.

polyhedron, two CdO6 octahedra, and one MoO4 tetrahedron in a −Cd2O7−Cd3O6−Cd3O6−Mo1O4− sequence, and the 6MR channels are constructed by two MoO4 tetrahedra, two TeO3 groups, and two CdO6 octahedra in a −Mo1O4− Te1O3−Cd1O6−Mo1O4−Te1O3−Cd1O6− sequence (type I) and by two CdO6 octahedra, two TeO3 groups, and two MoO4 tetrahedra in a −Cd1O6−Te2O3−Mo1O4−Cd1O6−Te2O3− Mo1O4− sequence (type II). 3.2. EDS Analysis and Powder X-ray Diffraction (PXRD). EDS analysis of Cd3(MoO4)(TeO3)2 indicated the presence of the Cd, Mo, Te, and O elements, with a Cd/Mo/ Te ratio of approximately 3:1:2 (Figure S1), which is in agreement with the results of crystal structural analysis. As shown in Figure S2, the experimental PXRD pattern agrees well with the simulated one originating from crystal structural data. 3.3. IR Spectroscopy. The IR spectrum of Cd3(MoO4)(TeO3)2 is provided in Figure S3. The characteristic bands of Cd3(MoO4)(TeO3)2 are similar to those of previously reported metal tellurites. The band at 898 cm−1 (w) confirms the presence of MoO4,39 and the band at 618 cm−1 (w) is assigned

Figure 3. Connection modes between Mo6+ and the anionic layer {Cd3Te2O10}∞6n− along the b axis. 11989

DOI: 10.1021/acs.inorgchem.6b02117 Inorg. Chem. 2016, 55, 11987−11992

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Inorganic Chemistry

grain size of about 105−150 μm), as shown in Figure S7 and that it is phase-matchable (Figure S8). The SHG response of Cd3(MoO4)(TeO3)2 is comparable to that of cadmium borophosphate Na3Cd3B(PO4)4 [1.1 × KDP (KH2PO4)].7 The NLO effect prompted us to analyze its structural origins. According to the structural analysis, the Mo1O4, Cd1O6, Cd3O6, and Cd2O7 polyhedra display obvious distortions. Each Te4+ cation (Te1 and Te2) present in the structure exhibits a distorted trigonal pyramid. The Te4+ cations exhibit asymmetric coordination environments that agree with those predicted by valence shell electron pair repulsion (VSEPR) theory.5 Therefore, the three types of asymmetric components should make contributions to the SHG response. To further confirm this conclusion, the directions and magnitudes of the dipole moments for the net polarization were calculated.49−52 The total polarization for Cd3(MoO4)(TeO3)2 (unit cell) and the respective contribution of the CdOn (n = 6, 7), MoO4, and TeO3 polyhedra are listed in Table 2. According to the

to Te−O−Mo asymmetric vibrations.40 Meanwhile, the two bands occurring about 558 and 452 cm−1 (both w) are attributable to Cd−O bonds. The peaks at about 795 and 690 cm−1 (both s) are clearly assigned to the Te−O vibrations of TeO3 units. Compared with the two characteristic bands of TeO2 [776 and 668 cm−1 (both s)], those of Cd3(MoO4)(TeO 3 ) 2 exhibit small blue shifts (19 and 22 cm−1 , respectively). This is due to the fact that the TeO3 groups are connected to MoO4 and CdOn (n = 6, 7) polyhedra in the structure of Cd3(MoO4)(TeO3)2. 3.4. UV−Vis Diffuse-Reflectance Spectroscopy. The UV−vis diffuse-reflectance spectrum of a Cd3(MoO4)(TeO3)2 crystalline sample was analyzed according to the Kubelka− Munk function39 F(R ) = (1 − R )2 /2R = α /S

where R, α, and S are the reflectance, absorption, and scattering, respectively. In the F(R)−E (eV) curve (Figure 6), the onset

Table 2. Directions and Magnitudes (in Debye) of the Dipole Moments of the CdO6, CdO7, MoO4, and TeO3 polyhedra in Cd3(MoO4)(TeO3)2 and Their Respective Contributions to the Unit Cell species Cd(1)O6 Cd(2)O7 Cd(3)O6 Mo(1)O4 Te(1)O3 Te(2)O3 CdOn (n = 6, 7) MoO4 TeO3 total

Figure 6. UV−vis diffuse-reflectance spectrum of Cd3(MoO4)(TeO3)2.

x (a) −2.53 −2.93 −5.52 −1.43 −23.04 −22.17 0 0 0 0

y (b) 1.12 −1.19 −0.18 1.10 −7.36 9.37 Unit Cell −0.52 2.20 4.02 5.70

z (c)

magnitude

0.28 −3.53 −1.79 −1.12 0.87 −15.41

2.86 3.99 5.24 1.87 24.46 24.49

0 0 0 0

0.52 2.20 4.02 5.70

calculated results, the polarizations of the CdOn (n = 6, 7), MoO4, and TeO3 groups are enhanced along the b axis (the total polarization for the unit cell has a positive value), whereas their polarizations are nearly offset along the a and c axes. These results reveal that the resultant SHG response should be attributed to the distorted CdOn (n = 6, 7), MoO4, and TeO3 polyhedra.

value is 3.81 eV for Cd3(MoO4)(TeO3)2, which is comparable to that of the compound Zn2(MoO4)(TeO3) (4.1 eV).39 This result is in accordance with the colorless nature of Cd3(MoO4)(TeO3)2 and its transparency at visible wavelengths. 3.5. Thermal Stability. The thermal stability of Cd3(MoO4)(TeO3)2 was investigated between 30 and 1400 °C (at a heating rate of 10 °C min−1 and with a gas flow of a dynamic N2 atmosphere of 0.1 L min−1). As shown in Figure S4, Cd3(MoO4)(TeO3)2 crystals are stable in the range of 30− 960 °C. The TG curve also shows a continuous weight loss starting from 960 °C and a significant endothermic peak at 1173 °C. These results reveal that Cd3(MoO4)(TeO3)2 has a very high thermal stability. To identify the composition of the final residual, the thermally decomposed residual was further characterized by powder XRD and IR spectroscopy (Figures S5 and S6). Unfortunately, the composition of the final product remains unknown because it could not be determined from the powder XRD pattern and IR spectrum. 3.6. SHG Measurements. Owing to the polar structure of Cd3(MoO4)(TeO3)2, it was necessary to investigate its NLO effects. We measured the SHG response of Cd3(MoO4)(TeO3)2 employing a Q-switched Nd:YAG solid-state laser. The results showed that the SHG response was approximately the same as that of microcrystalline KH2PO4 (KDP) (with a

4. CONCLUSIONS In summary, a new 3D cadmium molybdotellurite Cd3(MoO4)(TeO3)2 with 1D 4- and 6-MR channels was successfully obtained by means of the conventional solid-state method. Cd3(MoO4)(TeO3)2 was fully characterized by X-ray crystallography, IR spectroscopy, EDS analysis, and PXRD. The UV− vis diffuse-reflectance spectrum and TG curve revealed that Cd3(MoO4)(TeO3)2 exhibits a wide UV-transparent region and high thermal stability. This NCS compound has an SHG intensity that is approximately the same as that of KH2PO4 (KDP) (1.0 × KDP) at the same grain size of ca. 105−150 μm. This SHG response of Cd3(MoO4)(TeO3)2 can be attributed to its polar structure originating from the distorted TeO3 and MoO4 units and the displacements of d10 Cd2+ cations, a conclusion that was supported by dipole moment calculations. These results indicate that Cd3(MoO4)(TeO3)2 can act as a new potential candidate for an NLO material. Based on this successful work, we will continue to focus on searching for 11990

DOI: 10.1021/acs.inorgchem.6b02117 Inorg. Chem. 2016, 55, 11987−11992

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Inorganic Chemistry novel NLO crystal materials based on the CdO−AO3−BO2 system (A = Mo6+and W6+; B = Te4+ and Se4+).

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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.6b02117. CIF data for Cd3(MoO4)(TeO3)2 have been deposited at the Cambridge Crystallographic Data Centre (CCDC) (CCDC 1502123). They can be obtained free of charge from the CCDC at www.ccdc.cam.ac.uk/data_request/ cif. Selected bond lengths; results of BVS calculations for Cd, Mo and Te atoms; EDS spectrum of Cd3(MoO4)(TeO3)2; IR spectra and powder XRD patterns of Cd3(MoO4)(TeO3)2 and the thermally decomposed product; TG and DTG curves of Cd3(MoO4)(TeO3)2; SHG responses of Cd3(MoO4)(TeO3)2 and KDP; and phase-matching curves of of Cd3(MoO4)(TeO3)2 (PDF) Crystallographic data of Cd3(MoO4)(TeO3)2 (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Fax: +86-377-63513583. *E-mail: [email protected]. Fax: +86-377-63513583. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (Nos. 21571109, 21601095) and the Youth Project of Nanyang Normal University (No. QN17019).

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DOI: 10.1021/acs.inorgchem.6b02117 Inorg. Chem. 2016, 55, 11987−11992