Article pubs.acs.org/IC
Two Phosphates: Noncentrosymmetric Cs6Mg6(PO3)18 and Centrosymmetric Cs2MgZn2(P2O7)2 Yi-Gang Chen,† Mei-Ling Xing,† Peng-Fei Liu,§ Yao Guo,*,‡ Nan Yang,† and Xian-Ming Zhang*,† †
School of Chemistry & Material Science, Shanxi Normal University, Linfen, Shanxi 041004, China Department of Chemistry and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, China § 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 ‡
S Supporting Information *
ABSTRACT: Two new phosphatesCs 6 Mg 6 (PO 3 ) 18 (CMP) and Cs2MgZn2(P2O7)2 (CMZP)have been obtained, using high-temperature molten methods. Crystals of CMP with the polar P21 space group display a new threedimensional (3D) anionic framework possessing two onedimensional (1D) [PO3]∞ chains that are interconnected by isolated MgO6 octahedra, while CMZP with centrosymmetric monoclinic space group P2 1 /c possesses a new [MgZn2P4O20]14− structure unit consisting of two isolated P2O7 dimers, one ZnO4, and two disordered Mg/ZnO4 tetrahedral units. The polar phosphate CMP with deep-UV transparency (below 190 nm) shows weak second harmonic generation (SHG) response (0.1 × KDP), and the dipole moment analysis suggests that the weak SHG response mostly originates from much distorted CsOn polyhedron. Some related properties, such as optics, thermostability, and band structure derived from density functional theory, were explored.
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INTRODUCTION Crystals of nonlinear optical (NLO) response in producing light of deep ultraviolet (deep-UV) wavelengths ( 2σ(I))a
Cs6Mg6(PO3)18 2364.78 monoclinic P21 7.7437(4) 34.1273(17) 10.1063(5) 90 90.414(2) 90 2670.7(2) 2 2.941 4.793 2208 0.027(9) 1.047 0.0378, 0.0873 0.0400, 0.0899
Cs2MgZn2(P2O7)2 768.75 monoclinic P21/c 13.5270(14) 7.4464(8) 14.6905(15) 90 90.746(4) 90 1479.6(3) 4 3.451 8.635 1416 N/A 1.077 0.0292, 0.0859 0.0415, 0.1306
R1 = ∑||Fo| − |Fc||/∑|Fo|, and wR2 = [w(Fo2 − Fc2)2/w(Fo2)2]1/2.
Powder X-ray Diffraction. Their phase purities were confirmed by powder X-ray diffraction (XRD) diffraction analysis, which was performed on a Bruker Model D8 Avance powder diffractometer equipped with Cu Kα radiation (λ = 1.5418 Å) at room temperature. The scanning step width of 0.02° and scanning rate of 0.05° s−1 were applied to record the patterns in the 2θ range of 5°−70°. Infrared (IR) Spectroscopy. The Fourier transform infrared (FTIR) spectra were recorded from KBr pellets in the range 4000− 400 cm−1 on a Nicolet Model 5DX spectrometer. Ultraviolet-Visible Light (UV−vis) Diffuse Reflectance Spectroscopy. The ultraviolet−visible light−near infrared (UV-vis-NIR) diffuse reflection data were recorded at room temperature using a powdered BaSO4 sample as a standard (100% reflectance) on a Cary 5000 UV/vis/NIR spectrophotometer. The scanning wavelength ranged from 190 nm to 800 nm. Absorption (K/S) data were calculated using the following Kubelka−Munk function:27
crystals were successfully obtained under the same condition with the mixture of CsF, MgF2, ZnO, and NH4H2PO4 in the molar ratio of 4:1.5:1.5:6. After dissolving the yellow flux in water, a large number of colorless and block CMZP crystals were obtained (Figure 1b). The average atomic ratios of Cs:Mg:P and Cs:Mg:Zn:P in the title compounds, determined by energy-dispersive spectrometry (EDS), on several crystals were 1.0:1.0:3.1 and 2.1:1.2:1.9:4.1, respectively, which were in accordance with the determination from single-crystal X-ray structure analyses (Table S1 and Figure S1 in the Supporting Information). Pure polycrystalline samples of the two compounds were synthesized quantitatively by solid-state reactions. For CMP, amounts of CsF (0.410 g, 2.7 × 10−3 mol), MgF2 (0.186 g, 3.0 × 10−3 mol), and NH4H2PO4 (1.035 g, 9.0 × 10−3 mol) were thoroughly ground and pressed into pellets, whereas for CMZP, amounts of CsF (0.669 g, 4.4 × 10−3 mol), MgF2 (0.124 g, 2.0 × 10−3 mol), ZnO (0.324 g, 4.0 × 10−3 mol), and NH4H2PO4 (0.920 g, 8.0 × 10−3 mol) were pressed into pellets. The pellets were heated to 450 °C and dwelled in a muffle furnace for 10 h. The mixtures were then heated, to 700 °C for CMP and 740 °C for CMZP, and each then was sintered at that temperature for 36 h with several intermediate grindings. Their phase purities were confirmed by powder X-ray diffraction (XRD) diffraction. The measured XRD patterns well match the calculated XRD patterns based on single-crystal XRD analysis (see Figure S2 in the Supporting Information). Single-Crystal X-ray Diffraction. Data collections for CMP and CMZP crystals with dimensions of 0.4 mm × 0.15 mm × 0.1 mm and 0.4 mm × 0.35 mm × 0.2 mm were carried out on an Agilent Technologies Gemini EOS diffractometer with EOS CCD detector at 293 K using Mo Kα radiation (λ = 0.71073 Å). The collection of the
F(R ) =
(1 − R )2 K = 2R S
where R is the reflectance, K the absorption, and S the scattering. Thermal Behavior. Investigation of the thermal behavior was performed on a simultaneous TGA/DSC 1 STARe System thermal analyzer instrument (the DSC was calibrated with Al2O3). Each compound of ∼15 mg was placed in Al2O3 crucibles, heated at a heating rate of 10 K/min from 303 K to 1223 K. The measurements were carried out in an atmosphere of flowing N2. Second-Harmonic Generation. Powder second-harmonic generation (SHG) measurements were performed on the basis of the Kurtz−Perry method28 at 298 K. The measurements were carried out with a Q-switched Nd:YAG laser at a wavelength of 1064 nm and its SHG at 532 nm. Polycrystalline CMP samples were ground and sieved into a series of distinct size ranges: 25−40 μm, 40−63 μm, 63−80 μm, B
DOI: 10.1021/acs.inorgchem.6b02303 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry 80−125 μm, 125−150 μm, 150−200 μm, and 200−300 μm, which were pressed between glass slides and secured with tape in 1-mm-thick aluminum holders containing a hole 8 mm in diameter. Each of them was then placed into a light-tight box, and the intensity of the frequency-doubled output emitted from the samples was collected through a photomultiplier tube. Crystalline KH2PO4 (KDP) as the reference was ground and sieved into the same particle size ranges. The ratios of the SHG signals of CMP to the reference were calculated based on the intensity of second harmonic outputs in the same particle size range of 80−125 μm. Computational Method. The first-principles calculations of CMP and CMZP were performed by using the MedeA-VASP 5.3 package, based on the density functional theory (DFT).29 The plane-wave pseudo-potential (PWPP) method was employed in the study. The total energies were calculated within the generalized gradient approximation of Perdew−Burke−Ernzerhof (GGA-PBE) under the convergence criteria of 1 × 10−6 eV/atom. The plane-wave cutoff energy fixed at 800 eV was determined throughout the theoretical study. The tetrahedron smearing scheme was fulfilled for the integrations of Brillouin zone in electronic structure. The ion-electron interaction was achieved by the projector augmented wave (PAW) method. The valence electron configurations for Cs, P, Mg, Zn, and O are 5s5p6s, 2s2p3s3p, 2s2p3s, 3p3d4s, and 1s2s2p orbitals, respectively. The slab model was repeated under periodic boundary conditions with P1 symmetry. The k-point sampling of the Brillouin zone was carried out by the use of the Monkhorst−Pack method.30
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RESULTS AND DISCUSSION Crystal Structure. CMP is in the NCS space group P21 (No. 4), and Table 1 gives its fundamental crystal data. It exhibits a 3D framework composed of 2-fold helical [PO3]∞ chains and isolated MgO6 octahedra (Figure 2). The asymmetric unit contains 6 Mg, 6 Cs, 18 P, and 54 O atoms (Table S2a in the Supporting Information). All of these atoms occupy general positions. Therefore, the formula of CMP should be written as Cs6Mg6(PO3)18. Each highly distorted “seesaw-shaped” PO4 tetrahedron possesses two short lengths and two long P−O lengths, and the PO4 groups are further linked through corner-sharing to form two crystallographically independent 2-fold helical [PO3]∞ chains with a very long pitch of 34.1273(17) Å (Figure 2a). The lengths of P−O bond vary between 1.461(5) Å and 1.615(5) Å. Note that the two helical [PO3]∞ chains in the b-axis direction are bridged by Mg2+ ions via oxygen-shared atoms to form a 3D anionic framework exhibiting an ABCA′B′C′... packing structure, where A′, B′, and C′ layers rotate around the b-axis for 180° to the A, B, and C layer, respectively (Figure 2c). Obviously, the framework is a Blattice of pseudo translation. In other words, the 3D anionic framework in unit cell includes a three-layer arrangement and 21 helical axis in b-axis direction, which causes a long b-axis. It results in longer [PO3] chains in the unit cell than that of other phosphates such as ALa(PO3)4 (A = K, Cs),21,31 Cs6RE2(PO4)4 (RE = Y, Gd),32 APb2(PO3)5 (A = K, Rb, Cs),33 and similar silicates, such as FeSiO3,34 NaYSi2O6.35 Note that, although Cs2Mg2P6O18 (P213, No. 198 and Pc, No. 7, respectively)36 possesses the same general formula, CsMgP2O9 with CMP, the difference is that Cs2Mg2P6O18 features an isolated [P6O18]6− cyclohexaphosphate ring by the interconnection of six cornershared PO 4 tetrahedra (Figure S4 in the Supporting Information). Besides, the DSC measurement confirms no translation in CMP (Figure S5 in the Supporting Information). The Mg−O bond lengths and O−Mg−O angles vary between 2.017(5) Å and 2.138(5) Å and from 83.48(19)° to 178.1(2)°, indicating that the MgO6 octahedra are slightly distorted. Note that there are layered motifs within the ac-plane in the
Figure 2. Two crystallographically independent 2-fold helical [PO3]9 chains shown in purple and brown colors: (a) the 3D framework constructed by [PO3]∞chains, (b) MgO6 octahedra along the a-axis, and (c) MgO6 octahedra along the b-axis, showing 7-membered ring (7-MR) channels filled by Cs ions; (d) a 2D layered motif showing [MgP2O11]10− 3-membered ring (MRs) and [Mg3P4O31]36− 7-MRs in the ac-plane.
framework, where corner-sharing connection of MgO 6 octahedra and PO4 tetrahedra creates [MgP2O11]10− 3membered rings (3-MRs) and [Mg3P4O31]36− seven-membered rings (7-MRs) (Figure 2d). The Cs+ cations are located within 1D tunnels of 7-MRs (Mg3P4O31)36− (Figure 2d) and form asymmetric CsOn (n = 10, 12) polyhedra with distances of Cs− O bond varying 2.988(4) Å and 3.803(4) Å (Figure S3a in the Supporting Information). Bond valence sums29 for all atoms were analyzed and the total bond valences of Cs6Mg6(PO3)18 for Mg(1)−Mg(6), Cs(1)−Cs(6), P(1)−P(18), and O(1)− O(54) are 2.168−2.236, 0.792−0.880, 4.935−5.102, and 1.773−2.198, respectively (BVS, Table S2a in the Supporting Information). CMZP is located in the centrosymmetric space group P21/c (No. 14) and its asymmetric unit includes two Cs atoms, one Zn atom, four P atoms, two independent metal positions halfoccupied by Mg and Zn atoms, and 14 O atoms. In CMZP, partial substitution of Mg2+ at Zn2+ sites is preferential. Mg2+ has a four-coordinate effective ionic radius of 0.57 Å, which is almost equal to that of Zn2+ (0.59 Å), and thereby the crystallographic sites may jointly occupied by both cations. Changing the amount of the molar ratio such as 3:0.5:1:5 for CsF, ZnO, MgF2, and NH4H2PO4 resulted in the formation of the crystal CMP under the same conditions. In CMZP, the C
DOI: 10.1021/acs.inorgchem.6b02303 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry fundamental structure unit is a new [MgZn2P4O20]14− anion structure (Figures 3a and 3b) composed of two isolated P2O7
Because of isolated P2O7 dimers in CMZP, which is different from CMP, the existence of diphosphate units is verified by bridge vibrations of P−O−P. The bands located at 930 and 1150 cm−1 are derived from the bridge vibrations of P−O−P. The peak near 735 cm−1 could be related to O−P−O symmetric stretching and P−O−P asymmetric stretching. The IR spectrum further confirms the existence of diphosphate units.38 Thermal Stability. CMP and CMZP were investigated by using TGA and DSC under N2. As can be seen in Figures 4a
Figure 3. [MgZn2P4O20]14− structural units of Zn, Mg, and P atoms showing (a) two isolated P2O7 dimers, one ZnO4, and two Mg/ZnO4 tetrahedral units and (b) polyhedra chart in the b-axis direction; (c) 3D framework showing 8-MR tunnels filled by Cs ions along the baxis.
dimers, two Mg/ZnO4, and one ZnO4 tetrahedral units, and the neighboring structure units along the b-axis are connected by P2O7 dimers terminal O atoms to construct a 3D structural framework showing 8-MR tunnels filled by the Cs ions (Figure 3c). In the 3D anionic framework, the [MgZn2P4O20]14− structural unit by themselves extends wavily in the bc-plane and is interconnected by a c-glide plane (e.g., x, 3/4 − y, z) and 21 screw axes (1/4, 0, z), which results in an inversion center. Note that there are two types of P2O7 units in which P(1)O4 is connected with P(2)O4 by O(7) as the bridging oxygen, and P(3)O4 is linked with P(4)O4 (O(2) as the bridging oxygen), respectively. The [P2O7]4− dimers are separated from each other and operate themselves by the c-glide plane. The lengths of P−O bond vary between 1.487(5) Å and 1.629(4) Å. The four vertices of each Mg/ZnO4 or ZnO4 group are linked with four P2O7 dimers, and the distances of Mg/Zn−O bond and Zn−O bond vary between 1.904(4) Å and 1.943(4) Å, and between 1.917(4) Å to 1.955(4) Å, respectively. The Cs atoms are connected with 12 or 10 O atoms with lengths of Cs−O bond varying between 3.101(4) Å and 3.689(4) Å (Figure S3b in the Supporting Information). Bond valence sum calculations37 resulted in values of 2.209, 2.225, 2.209, 0.917−1.015, 4.996−5.135, and 1.964−2.077 for Mg, Zn(1), Zn(2) Cs(1)− Cs(2), P(1)−P(4), and O(1)−O(14), respectively (Table S2b in the Supporting Information). Infrared Spectroscopy. The phosphate geometries in the two compounds can be determined by IR spectroscopy (see Figure S6 in the Supporting Information). For CMP, the intense peak at ∼1280 cm−1 is attributed to the asymmetrical stretching vibration of O−P−O, while the peaks near 1000 and 1166 cm−1 are considered to be due to the symmetrical O−P− O stretching vibration. Asymmetrical stretching vibration of P− O−P with the sharp peaks is located at 858 and 950 cm−1, whereas a few peaks between 640 and 800 cm−1 are assigned to the symmetrical P−O−P stretching vibration. Symmetrical O− P−O and P−O−P bending vibrations are revealed by a few peaks between 563 and 424 cm−1. The IR results are in accordance with the reported result of (PO3)nn− chains.21
Figure 4. TGA and DSC curves of the polycrystalline (a) CMP and (b) CMZP.
and 4b, the TGA and DSC curves of the polycrystalline CMP and CMZP demonstrate no weight loss from room temperature to 900 °C. Melting endothermic absorption peaks at 859.7 and 910.3 °C are observed for CMP and CMZP, respectively, which again confirms that the phosphates possess good thermal stability. UV−vis-NIR Spectroscopy. The spectra of CMP and CMZP between 190 and 800 nm are exhibited in Figure S7 in the Supporting Information. As shown in Figure S7, the UV cutoff edges of CMP and CMZP are obviously below 190 nm (equivalent band gap: 6.52 eV). Even at 190 nm, the reflectance is ∼40% for the two compounds. Theoretical Calculation. In order to probe the mechanism of optical properties of CMP and CMZP, DFT methods were used to carry out theoretical calculations. The electronic band structures of CMP and CMZP were achieved (Figure S8 in the Supporting Information), indicating that both compounds are indirect band gap materials with band gaps of 5.36 ev and 4.98 eV for CMP and CMZP, respectively. Because of the DFT limitation, the calculated band gap is always underestimated.39 The densities of states (DOS) are shown in Figures 5a and 5b. For CMP (Figure 5a), it is clear that the upper part of valence band (VB) from −7.0 eV to the valence band maximum chiefly consists of the O 2p and P 3p orbitals, meaning that P−O bonds are relatively strong covalent bonds. And the rest, from −7 eV to −20 eV scarcely interact with adjacent atoms, D
DOI: 10.1021/acs.inorgchem.6b02303 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
chains are separately calculated (see Table 2); their net dipole moments are only 2.54 and 6.45 D, respectively, which are comparable to the dipole moments of PO4 tetrahedra in CMP (∼4−6 D; Table S4 in the Supporting Information), and the total dipole moment of the two chains is 3.93 D. Therefore, the dipole moments associated with PO4 tetrahedra have mostly been cancelled out. Based on structural data, the distortion of MgO6 octahedron is very small, so it is to be expected that net dipole moments of MgO6 octahedra (the detailed calculation results are listed in Table S4) only have a value of 2.29 D. Note that the alkali-metal oxygen polyhedra have relatively larger dipole moments of 11.64 D, implying that the CsOn polyhedra (n = 10, 12) have much more distortion, as shown in the Supporting Information. As a result, that is to say, the contribution of CsOn polyhedral to SHG should be very significant. In addition, because of the symmetry of the 21 helical axis, a net distortion for CMP should be along the y-axis direction. The total dipole moment of the entire cell unit (Z = 1) is 13.33 D, and it is basically along the y-axis direction. Furthermore, since the compound belongs to point group 2, there are four independent nonvanishing second-order nonlinear optical susceptibility tensors (d31, d32, d33, and d36; d14 = d25 = d36; d15 = d31; d24 = d32) under the restriction of Kleinman’s symmetry. At 532 nm (corresponding band gap: 2.33 eV), the dave, which is defined as
Figure 5. Densities of states (DOS) for (a) CMP and (b) CMZP.
consisting of isolated inner-shell states with Cs 5s, P 2s2p, Mg 2s, and O 2s orbitals. The conduction band (CB) bottom is composed of a mixture of all constituent atomic orbitals. The optical response resulting chiefly from electronic transitions between the VB and CB bands is close to the band gap, so the condensation of [PO4]3− tetrahedral units which built the 1D [PO3]∞ chains chiefly determines the magnitude of the band gap of CMP. For CMZP (Figure 5b), the remarkable difference from CMP is that the Zn 3d states from ZnO tetrahedra and Zn/MgO4 tetrahedra provide the considerable contributions to the VB top and CB bottom, which results in a narrower band gap. Nonlinear Optical (NLO) Response. Since CMP crystallizes in a polar space group, its SHG reponse is explored. Using a light source at 1064 and 532 nm, CMP and KDP SHG responses were measured. SHG measurements showed that CMP displays a very weak response in the visible region, whereas in the UV region, CMP belongs to type-I phasematchable, with a weak SHG intensity of ∼10% of that of KDP (0.1 × KDP; see Figure S9 in the Supporting Information). This relative intensity is comparable to most of the deep-UV NLO phosphate crystals, such as Rb2Ba3(P2O7)2 (0.3 × KDP), KLa(PO3)4 (0.7 × KDP), Ba3P3O10Cl (0.6 × KDP), Ba5P6O10 (0.8 × KDP).18−21 In order to further analyze the SHG origin of CMP, calculation of the local dipole moments of CsOn, MgO6, and PO4 polyhedra is performed by a bond-valence approach,40 and the corresponding results are demonstrated (see Table 2). Since the unit cell (Z = 1) contains two 1D [PO3]∞chains that are constructed through P(1)O4−P(9)O4 and P(10)O4− P(18)O4 tetrahedra, respectively, the dipole moments of two
dave =
is calculated to be 0.17 pm/V for the title compound, which is much smaller than the d36 value of KDP (1.15 pm/V), which generally agrees with the experiment result (see Figure S10 in the Supporting Information).
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Dipole Moment (Debye) x
y
z
total magnitude
∑9k=1(PO4)k ∑18 k=10(PO4)k ∑18 k=1(PO4)k ∑6k=1(MgO6)k ∑6k=1(CsOn)k total
2.3967 −6.2470 −3.8503 −1.0143 2.6335 −2.2311
−0.1941 0.2459 0.0518 −1.9996 −11.1810 −13.1288
0.8048 −1.6052 −0.8004 −0.4795 1.8928 0.6129
2.5356 6.4546 3.9329 2.2929 11.6419 13.3312
CONCLUSION
In summary, two new phosphatesCs6Mg6(PO3)18(CMP) and Cs2MgZn2(P2O7)2(CMZP)have been achieved through high-temperature molten method. Crystals of CMP with an acentric P21 space group exhibit a new three-dimensional (3D) anionic framework containing two one-dimensional (1D) [PO3]∞chains, which are interconnected by isolated MgO6 octahedra, whereas CMZP with the centrosymmetric monoclinic space group P21/c possesses a new [MgZn2P4O20]14− structure unit consisting of two isolated P2O7 dimers, two disordered Mg/ZnO4 and one ZnO4 tetrahedral units. In CMZP, the existence of the c-glide plane results in an inversion center, and finally CMZP crystallizes in a centrosymmetric space group; almost equal in effective ionic radius brings about partial substitution of Mg2+ at Zn2+ sites, which forms the disordered Mg/ZnO4 tetrahedra. Second harmonic generation (SHG) measurement of polycrystalline CMP powder indicates that the SHG response is very weak in the visible region, while the SHG intensity is 10% of that of KDP in the ultraviolet (UV) region, and, meanwhile, it is phase-matchable. Dipole moment analysis suggests that its weak SHG response chiefly originates from much distorted CsOn polyhedron rather than obviously asymmetric PO4 polyhedra. Evidently, the UV cutoff edge of CMP is below 190 nm, which is chiefly attributed to the electronic transitions between the O and P atoms. In the future, we will further explore and design highly nonlinear optical (NLO)-active materials by incorporating a planar π-conjugated system while maintaining deep-UV transparency, and then we will investigate the polar mechanism.
Table 2. Dipole Moments of the CsOn, MgO6, and PO4 Polyhedra
polar units
2d31 + 2d32 + d33 + 3d36 8
E
DOI: 10.1021/acs.inorgchem.6b02303 Inorg. Chem. XXXX, XXX, XXX−XXX
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ASSOCIATED CONTENT
S Supporting Information *
CIF files, The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ acs.inorgchem.6b02303. Band structures, DSC, optical measurement, XRD patterns, atom coordination environments, bond angles and distances for both compounds CMP and CMZP (PDF) Crystallographic data files for both compounds CMP and CMZP (CIF)
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AUTHOR INFORMATION
Corresponding Authors
*Fax: +86 372 2909732. E-mail:
[email protected]. *Fax: +86 357 2051402. E-mail:
[email protected]. ORCID
Xian-Ming Zhang: 0000-0002-8809-3402 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The subject was financially supported by the Plan for 10 000 Talents in China, National Science Fund for Distinguished Young Scholars (No. 20925101) and Shanxi Province Foundation for Key Subject.
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REFERENCES
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