Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as

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Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as Potential Ultraviolet Nonlinear Optical Materials Miriding Mutailipu, Zhiqing Xie, Xin Su, Min Zhang, Ying Wang, Zhihua Yang, Muhammad Ramzan Saeed Ashraf Janjua, and Shilie Pan J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b11263 • Publication Date (Web): 21 Nov 2017 Downloaded from http://pubs.acs.org on November 22, 2017

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Journal of the American Chemical Society

Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as Potential Ultraviolet Nonlinear Optical Materials

Miriding Mutailipu,†,‡,# Zhiqing Xie,†,# Xin Su,§ Min Zhang,†,* Ying Wang,†,* Zhihua Yang,† Muhammad Ramzan Saeed Ashraf Janjua,ξ Shilie Pan†,*

†Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences; Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China ‡University of the Chinese Academy of Sciences, Beijing 100049, China §Xinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matter Physics, College of Physical Science and Technology, Yili Normal University, Yining, Xinjiang 835000, China ξ Chemistry Department, King Fahd University of Petroleum and Minerals (KFUPM), Dhahran 31261, Kingdom of Saudi Arabia

*Corresponding authors, E-mails: [email protected]; [email protected]; [email protected]

Abstract Chemical cosubstitution strategy was implemented to design the potential ultraviolet (UV) and deep-UV nonlinear optical (NLO) materials. Taking the classic β-BaB2O4 as a maternal structure, by simultaneously replacing the Ba2+ and [B3O6]3units for monovalant (K+), divalent (alkaline earth metal), trivalent (rare-earth metal, Bi3+) ions, and the [B5O10]5- clusters through two different practical routes, altogether twelve new mixed-metal noncentrosymmetric borates K7MIIRE2(B5O10)3 (MII = Ca, Sr, Ba, K/RE0.5; RE = Y, Lu, Gd) as well as K7MIIBi2(B5O10)3 (MII = Pb, Sr) were successfully designed and synthesized as high-quality single crystals. The selected K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3 compounds were performed all-round characterizations via experimental and theoretical ways. They all exhibit suitable second-harmonic generation (SHG) responses as large as the commercial KH2PO4 (KDP) and short UV cutoff edges. These results confirm the feasibility of chemical cosubstitution strategy to design NLO materials and the three seclected crystals may have potential application as UV NLO materials.

1

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1. Introduction The last several decades have witnessed the astounding progress in the exploration and design of the ultraviolet (UV; λ < 400 nm) and deep-UV (λ < 200 nm) nonlinear optical (NLO) materials as they can satisfy the constantly growing demands for multiple technological applications.1-6 From the sustained efforts of many chemists and materials scientists to discover the NLO materials with remarkable properties, several chemical systems, like borates,7-9 phosphates,10-12 carbonates,13-15 and nitrates,16 etc,17-20 have been considered as the alternative systems for searching the UV and deep-UV NLO materials. With respect to borates, they reveal a wide optical transparency window, varied acentric structure types, high laser damage thresholds, and large polarizability.21-25 As such, several commercial borate-based NLO materials have been developed, including β-BaB2O4 (β-BBO),26 LiB3O5 (LBO),27 and KBe2BO3F2 (KBBF),28 etc. Among borates, alkali and alkaline earth metals are the preferred alternative elements for designing borate-based NLO materials, mainly because those selected cations are free of d−d or f−f electronic transitions, which is beneficial to have a good transparency in UV even deep-UV spectral region.3,29 As a result, a variety of mixed alkali or/and alkaline earth metal borates, BaAlBO3F2,30 Na2CsBe6B5O15,31 Li4Sr(BO3)2,32 and K3B6O10X (X=Br, Cl),33,34 etc, were continuously reported as the front-line candidates for the UV or deep-UV NLO materials. From the electronic configuration point of view, several trivalent rare-earth cations RE3+ (RE = Sc, Y, La, Gd, and Lu) with closed-shell electronic configurations or half-occupied 4f orbitals are also suitable, which will effectively inhibit the unfavorable d−d or f−f electronic transitions and broaden the transparency window.35-46 Besides, the rare-earth cations coordinated into RE-based deformed polyhedra with relatively large hyperpolarizability can enhance the second-harmonic generation (SHG) responses. For example, the distorted YO6 octahedra, as the dominant NLO active microscopic units in YAl3(BO3)4, improved the second order optical susceptibility.35 In view of the aforementioned advantages, rare-earth borates 2


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RECa4O(BO3)3 (RE= Y, Gd),36-38 Na3La9O3(BO3)8,39,40 and La2CaB10O19,41 show short UV cut-off edges and suitable SHG coefficients. In addition to select the appropriate cations, how to effectively design NLO materials with presupposed structures or properties is also critically important.47,48 Recently, cosubstitution strategy has been proved to be an effective way to design new functional materials based on the known classical compounds, which can reorganize the crystal structures by simultaneously replacing two (or more) ions and fundamental building units, etc.49-52 Based on the chemical cosubstitution strategy, Na3Ba2(B3O6)2F (NBBF) can be structurally considered as the derivatives of cosubstituting the Ba2+ atoms in α-BBO for 3Na+ and F- atoms in NBBF.50,53 Similarly, BaAlBO3F230 was derived from simultaneously replacing K+ and 2Be2+ groups in KBBF for Ba2+ and Al3+, which result in the transformation from beryllium borate-based NLO materials to beryllium-free ones. Also inspired by the [BO3]3groups can occupy the sites of the [PO4]3- units in apatite Ca5(PO4)3F, Ca5(BO3)3F54 was discovered, which can be considered as the results of cosubstitution behaviors among different anionic building blocks and can also realize the mutual transformation between borates and phosphates. The similar cosubstitution manners can also occur between [PO4]3- and [VO4]3-, [BO3F]4 and [BeO3F]5 , [NbO6]7- and −

−

[TiO5F]7-, [3F-] and [BO3]3-, etc.55-58 Guided by these ideas above, taking classic β-BBO as a maternal structure, by cosubstituting the cationic parts of β-BBO for multiple rare-, alkali-, and alkaline-earth metals, altogether twelve new noncentrosymmetric borates were successfully designed and synthesized. For the anionic units, the isolated [B5O10]5double rings in these derivatives can be considered as the recombination of two [B3O6]3- single rings in β-BaB2O4 through a shared B atom. In this paper, we select K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3 as representatives to give them all-round characterizations by experimental and theoretical ways. Results show that all the three selected compounds exhibit suitable SHG responses and short UV cutoff edges, indicating that they may have potential applications as NLO materials ranging from the UV to the near-IR region. 3



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2. Experimental section 2.1 Reagents All the raw materials including KF, K2CO3, MIIF2 (MII = Ca, Sr, Ba), MIICO3 (MII = Ca, Sr, Ba), RE2O3 (RE = Y, Lu, Gd), Bi2O3, and B2O3 were purchased from Shanghai Aladdin Bio-Chem Technology Co., LTD as K, MII, RE, Bi, and B-based reactants for the expected K7MIIRE2(B5O10)3 (MII = Ca, Sr, Ba, K/RE0.5; RE = Y, Lu, Gd) and K7MIIBi2(B5O10)3 (MII = Pb, Sr) phases, respectively. 2.2 Single crystal preparation and the synthesis of title compounds The single crystals of K7MIIRE2(B5O10)3 (MII = Ca, Sr, Ba; RE = Y, Lu, Gd) and K7MIIBi2(B5O10)3 (MII = Pb, Sr) were obtained by the high-temperature solution reaction by mixing KF, MIIF2, RE2O3(or Bi2O3), and B2O3 according to a molar ratio of 14-17:2-5:2-5:15-17. While for the targeted K7.5RE2.5(B5O10)3 (RE = Y,

Gd),

the

molar

ratios

of

the

loaded

reactants

are

KF:

RE2O3:B2O3=15-17:3-5:15-17. Those raw reagents were mixed homogeneously and placed into the platinum crucibles. Then the samples were heated to 850 °C at a rate of 50 °C/h and held at this selected temperature for 24 hours to melt thoroughly, after that, cooled to 750 °C at a rate of 1 °C/h, and then cooled to 30 °C at a rate of 20 °C/h. The final colorless and transparent single crystals were formed in the stage of crystallization, which can be manually picked out from reaction products for further determining the microscopic single crystal structures. Polycrystalline

samples

of

K7CaY2(B5O10)3,

K7SrY2(B5O10)3,

and

K7BaY2(B5O10)3 were synthesized via solid-state reaction method by mixing K2CO3, MIICO3 (MII = Ca, Sr, Ba), Y2O3, and B2O3 according to the ratio of 3.5: 0.9: 0.8: 7.5. The mixtures were preheated at 400 °C for 48 hours. After that, the temperature was gradually raised to 820, 780, 760 °C for the Ca-, Sr-, Ba-based compounds, respectively. Accompanied with several intermediate grindings and mixings, and then held for 72 hours. With this procedure, the pure polycrystalline samples of three targeted compounds were successfully obtained. 4


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Through many experiments on searching for the suitable fluxes (Table S1 in the Supporting Information), the single crystal of K7BaY2(B5O10)3 was final grown by the top-seeded solution growth method with KF as the flux. The pure polycrystalline samples of K7BaY2(B5O10)3 as well as KF were mixed according to the molar ratio of 1:3.2 and heated to 870 °C in 24 hours. And a seed obtained from the earlier stage of spontaneous crystallization was introduced into the solution with a rotation rate of 5 rpm. Then the temperature was slowly decreased to 789 °C at a rate of 1 °C/h. Then the solution was cooled to 786 °C at a cooling rate of 1 °C/day. When the crystal growth process was done, the as-grown crystal was pulled from the solution and cooled (20 °C/h) to room temperature. With this procedure, millimeter scale single crystals of K7BaY2(B5O10)3 were obtained (Figure S1 in the Supporting Information). 2.3 Thermal behavior analysis Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) of K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3 were investigated using a NETZSCH STA 449C simultaneous thermal analyzer. The samples were placed in a platinum crucible and heated at a rate of 5 °C/min from 40 to 1000 °C, and then cooled to 200°C at a rate of 5 °C/min under flowing of N2. 2.4 Powder X-ray diffraction Powder X-ray diffraction (PXRD) measurements for targeted K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) were carried out on a Bruker D2 PHASER diffractometer equipped with Cu Kα radiation at room temperature. The 2θ range is 10–70° with a step size of 0.02° and a fixed counting time of 1 s/step. 2.5 Structure determination The single crystals of K7MIIRE2(B5O10)3 (MII = Ca, Sr, Ba, K/RE0.5; RE = Y, Lu, Gd) and K7MIIBi2(B5O10)3 (MII = Pb, Sr) were mounted on a glass fiber for data collection by single crystal XRD on an APEX II CCD diffractometer equipped with monochromatic Mo Kα radiation at room temperature. The reductions of the collected data were performed with the Bruker Suite software package. The numerical absorption corrections were carried out with the SADABS program and integrated 5



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with the SAINT program.59 The structures were established by the direct method with program SHELXS and refined by the full-matrix least-squares program SHELXL.60 The final solved structures were rechecked by the program PLATON for verifying the probable missing symmetric elements,61 but no higher symmetries were recommended. During the refinement section of this series structures, we found that the K(1) and Y(2) atoms in K7.5Y2.5(B5O10)3, K(1) and Gd(2) atoms in K7.5Gd2.5(B5O10)3 were in substitution disorder. Therefore, judging from the atomic thermal displacement parameters and charge balance principles, the K(1) and Y(2), K(1) and Gd(2) atoms in structures of K7.5Y2.5(B5O10)3 and K7.5Gd2.5(B5O10)3 were set to share the same sites with a disorder ratio of 1:1, which can help us to get the relatively better residual (R) values

and

reasonable

equivalent

isotropic

displacement

parameters.

The

crystallographic data are listed in Table 1. The related crystal data, including selected bond lengths and atomic coordinates equivalent isotropic displacement parameters are listed in Tables S2-S25 in the Supporting Information, respectively. 2.6 Vibrational spectroscopy and optical properties The infrared spectroscopy was carried out on a Shimadzu IRAffinity-1 spectrometer in order to specify and compare the coordination of the B atoms in K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba). The samples were mixed with dried KBr, and then collected in the range from 400 to 4000 cm-1 with a resolution of 2 cm-1. The UV-vis-NIR

diffuse-reflectance

data

for

the

polycrystalline

powders

of

K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) were collected by a Shimadzu Solid Spec-3700DUV Spectrophotometer with the measurement range extended from 190 to 2500 nm. 2.7 Powder second-harmonic generation measurements The powder SHG measurements for targeted K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) were carried out on the basis of the Kurtz–Perry method at room temperature.62 A Q-switched Nd:YVO4 solid-state laser were selected as the source of the radiation at λω = 1064 nm, and the radiation was doubled to second harmonics λ2ω = 532 nm. The crystal aggregates were ground and sieved into a series of distinct size ranges: 20–38, 38–55, 55–88, 88–105, 105–150, 150–200, and 200–250 µm, which were placed into 6


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a light-tight box and irradiated with the laser. The intensities of the frequency-doubled output emitted from the samples were collected by a photomultiplier tube. The commercial NLO crystal KDP was also ground and sieved into the same particle size range for the reference. 2.8 Calculation details The electronic structures calculations were performed using a plane-wave basis set and pseudopotentials within density functional theory (DFT) was also implemented in the total-energy module CASTEP.63 The exchange and correlation effects were treated by Perdew–Burke–Ernzerhof (PBE) in the generalized gradient approximation (GGA).61 The interactions between the ionic cores and electrons were described by norm-conserving pseudopotentials.64 The following orbital electrons were treated as valence electrons: K 3s2 3p6 4s1, Ca 3s2 3p6 4s2，Sr 4s2 4p6 5s2, Ba 5s2 5p6 6s2，Y 4d1 5s2, B 2s2 2p1, and O 2s2 2p4. The number of plane waves included in the basis was determined by a cutoff energy of 540 eV, and the numerical integration of the Brillouin zone was performed using a 4 × 4 × 4 Monkhorst–Pack scheme k-point grid sampling for K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3. 3. Results and discussion 3.1 Synthesis and thermal behavior During the synthesis process of the pure polycrystalline samples, we tried to obtain the pure phases of K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) according to the stoichiometric ratio via traditional solid-state reactions method. Unfortunately, before melting at about 1000 oC, the observed XRD patterns confirm the coexistence of targeted K7MIIY2(B5O10)3 phases and YBO3 (PDF No. 32-1428), which is doomed to have some inaccurate results during the physicochemical properties tests. Faced with this, several attempts have been paid to improve the purity, including changing the raw materials, adjusting the molar ratios, using other synthetic methods (molten salt and sol-gel method), changing the temperature program, etc. Finally, the pure polycrystalline samples of K7MIIY2(B5O10)3 were successfully obtained by mixing the raw materials via solid-state reactions method according to the molar ratio of K2CO3: MIICO3 (MII = Ca, Sr, Ba): Y2O3: B2O3 = 3.5: 0.9: 0.8: 7.5. As shown in Figure 1a, the 7



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Table 1. Crystallographic data for this series compounds Empirical formula

K7CaY2B15O30

K7SrY2B15O30

K7BaY2B15O30

K7CaLu2B15O30

K7SrLu2B15O30

Formula weight

1133.75

1181.29

1231.01

1305.87

1353.41

K7BaLu2B15O30 1387.02

Crystal system

Trigonal

Trigonal

Trigonal

Trigonal

Trigonal

Trigonal

Space group

R32

R32

R32

R32

R32

R32

a (Å)

13.2182(18)

13.1142(18)

12.9884(15)

13.1433(10)

13.0208(14)

12.9705(15)

c (Å)

14.949(4)

15.319(4)

15.718(4)

14.905(2)

15.297(3)

15.651(4)

Z

3

3

3

3

3

3

Volume (Å3)

2262.0(8)

2281.6(8)

2296.4(6)

2229.9(4)

2246.1(6)

2280.3(6)

F(000)

1638

1692

1746

1830

1884

1914

Completeness

100%

99.8%

99.7%

100%

99.5%

99.7%

GOF on F2

0.971

0.961

1.099

1.096

1.095

1.112

-0.020(7)

-0.001(10)

0.000

-0.012(17)

0.017(15)

0.000

Absolute structure parameter Final R indices

R1 = 0.0236,

R1 = 0.0265,

R1 = 0.0508,

R1 = 0.0213,

R1 = 0.0205,

R1 = 0.0351,

[Fo2>2σ(Fo2)]a

wR2 = 0.0477

wR2 = 0.0575

wR2 = 0.1367

wR2 = 0.0569

wR2 = 0.0587

wR2 = 0.0938

R indices (all data) a Empirical formula

R1 = 0.0271,

R1 = 0.0323,

R1 = 0.0549,

R1 = 0.0221,

R1 = 0.0211,

R1 = 0.0365,

wR2 = 0.0488

wR2 = 0.0596

wR2 = 0.1400

wR2 = 0.0574

wR2 = 0.0590

wR2 = 0.0947

K7CaGd2B15O30

K7SrGd2B15O30

K7.5Y2.5B15O30

K7.5Gd2.5B15O30

K7PbBi2B15O30

K7SrBi2B15O30

Formula weight

1270.43

1317.97

1160.35

1328.71

1541.00

1421.43

Crystal system

Trigonal

Trigonal

Trigonal

Trigonal

Trigonal

Trigonal

Space group

R32

R32

R32

R32

R32

R32

a (Å)

13.310(4)

13.148(2)

13.142(2)

13.264(6)

13.331(2)

13.2512(19)

c (Å)

15.005(8)

15.417(5)

15.099(5)

15.282(14)

14.910(5)

15.288(4)

Z

3

3

3

3

3

3

Volume (Å )

2302.1(15)

2308.2(9)

2258.3(9)

2329(3)

2294.6(10)

2324.8(8)

F(000)

1788

1842

1119

1194

2088

1956

Completeness

100%

100%

100%

99.9%

99.6%

100%

GOF on F2

1.052

1.055

1.017

1.021

1.134

1.068

-0.01(2)

0.048(15)

-0.022(14)

-0.004(17)

0.000

0.001(9)

3

Absolute structure parameter Final R indices

R1 = 0.0237,

R1 = 0.0192,

R1 = 0.0392,

R1 = 0.0209,

R1 = 0.0426,

R1 = 0.0195,

[Fo2>2σ(Fo2)]a

wR2 = 0.0607

wR2 = 0.0391

wR2 = 0.0855

wR2 = 0.0433

wR2 = 0.1182

wR2 = 0.0437

R indices (all data) a a

R1 = 0.0241,

R1 = 0.0206,

R1 = 0.0547,

R1 = 0.0221,

R1 = 0.0435,

R1 = 0.0217,

wR2 = 0.0610

wR2 = 0.0396

wR2 = 0.0913

wR2 = 0.0441

wR2 = 0.1194

wR2 = 0.0488

R1 = Σ||Fo| - |Fc||/Σ|Fo| and wR2 = [Σw(Fo2 – Fc2)2 / Σw Fo4]1/2 for Fo2 > 2σ( Fo2)

8


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observed XRD patterns are in good agreement with the corresponding theoretical ones.

Figure 1. Powder X-ray diffraction patterns (a) and TG-DSC curves (b) of K7CaY2(B5O10)3, K7SrY2(B5O10)3, K7BaY2(B5O10)3.

Thermal

stabilities

of

selected

K7CaY2(B5O10)3,

K7SrY2(B5O10)3,

K7BaY2(B5O10)3 polycrystalline samples were evaluated by TG and DSC. For each of the three compounds, just only one endothermic peak can be observed on the heating part of the DSC curves and no obvious weight loss on their TG curves in the range from 40 to 1000°C, which tentatively proves that the tested compounds can be stable at least up to 965, 946 and 922°C, respectively (Figure 1b). While there are no any peaks on the cooling part of DSC curves, which is caused by the high viscosity of the B-rich systems and can be confirmed by the glassy products of the tested samples. Till now, whether K7MIIY2(B5O10)3 series belong to congruent melting compounds or not is still unknown just only based on the results of TG and DSC. Therefore, the polycrystalline samples (2.0 g) of K7MIIY2(B5O10)3 were placed into platinum crucible and heated to 1000 °C for melting homogeneously, then cooled to room temperature very slowly (1.0°C/h). The PXRD patterns of the residues show different diffraction patterns from those of the initial powders (Figures S2-S4 in the Supporting Information), which indicates that those compounds melt incongruently and the suitable flux should be introduced to decrease the temperature during the crystal growth. Obvious 9



inclusions were observed in the as-grown K7BaY2(B5O10)3 crystal, indicating that more suitable growth process parameters (flux, the orientation of seed, and temperature fields, etc) should be further explored. Therefore, the crystal growth of the related compounds will also be ongoing with the motive of our crystals being used as UV nonlinear optical. 3.2 Crystal structure description Crystallographic analysis reveals that all the twelve reported borates are isostructural and crystallize in the same noncentrosymmetric trigonal space group,

R32, with only slightly differences in the related unit cell parameters. The volumes increases continuously from Ca-, Sr- to Ba-based compounds with the decreasing of a values and increasing of c values in two series K7MIIRE2(B5O10)3 (MII = Ca, Sr, and Ba; RE = Y and Lu ), respectively. The ball-and-stick typological view of the frameworks are shown in Figure 2a, which present to be a three-dimensional (3D) framework composed of KO6, MIIO6 (MII = Ca, Sr, Ba), REO6 (RE = Y, Lu, Gd, K/RE) or BiO6 octahedra, and isolated [B5O10]5- clusters. The asymmetric unit of K7MIIRE2(B5O10)3 contains three, one, one, three, and five crystallographic independent K, MII, RE, B, and O atoms, respectively. With respect to the B-O structural framing, the B(1, 2) and B(3) atoms are three and four coordinated with O atoms into the triangular [B(1,2)O3]3− and tetrahedral [B(3)O4]5− units, respectively. The centered [B(3)O4]5− group is surround by two pairs [B(1,2)O3]3− groups to form a [B5O10]5- cluster, (Figure 2c) which are arranged in isolated configuration without connecting with any other B or B-containing units. While for the RE atoms, they are six-coordinated for the REO6 octahedra, which continuously share its four of six equatorial oxygens with the nearest [B5O10]5- units to form a RE-B-O based single layer (Figures 2d and 2e), then those single layers are further connected to form double layers. Further, the whole 3D structures are stacked through the connection of the RE-O bonds and the [B5O10]5- clusters in approximately vertical manner between double layers. The K and MII atoms are identically six-coordinated, forming the KO6, MIIO6 octahedra and filling into the interstice between those RE-B-O based layers. Besides, the topology of K7MIIRE2(B5O10)3 series can be simplified by considering 10


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the [B5O10]5- clusters and the REO6 octahedra as four-connected (4-c) and 6-c nodes (Figure 2b). As a result, hea-type topological 4, 6-c 2-nodal net is formed with the Schläfli symbol of {43;63}3{46;69}2 for this series structures.

Figure 2. Crystal structure of K7MIIRE2(B5O10)3. (a) The whole crystal structure of K7MIIRE2(B5O10)3 viewed along c axis. (b) Topological representation of K7MIIRE2(B5O10)3, the [B5O10]5- and REO6 basic units are regarded as 4-c and 6-c nodes. (c) The [B5O10]5- communities. (d) The layered structures of K7MIIRE2(B5O10)3. (e) The RE-B-O based single layer in K7MIIRE2(B5O10)3.

Figure 3. Structural similarity between β-BaB2O4 (left) and K7MIIRE2(B5O10)3 (right) 11



From a chemical point of view, the K7MIIRE2(B5O10)3 and K7MIIBi2(B5O10)3 series can be regarded as the derivatives of cosubstitution strategy based on β-BaB2O4. (Figures 3 and 4) When making the stoichiometry of β-BaB2O4 expand to fifteen times than that of original value, resulting in Ba7Ba2Ba6(B3O6)5. Based on this, two practical routes are given from maternal structures to derivatives: 15Ba2+= 14K++ 2M2+ + 4RE3+(or 4Bi3+) and 15Ba2+= 14K++ K/RE+ + 4RE3+; (1) [Ba7]14+, [Ba2]4+, and [Ba6]12+ are respectively replaced by the K14, Mଶ୍୍, and Mସ୍୍୍ units with the same chemical valance states, resulting in K7MIIMଶ୍୍୍ B15O30, where MII is the divalent Ca2+, Sr2+ and Ba2+, MIII is the trivalent rare-earth Y3+, Lu3+, Gd3+ for the derivatives K7MIIRE2(B5O10)3, while MII and MIII is the divalent Pb2+, Sr2+ and trivalent Bi3+ for the derivatives K7PbBi2(B5O10)3 and K7SrBi2(B5O10)3, respectively; (2) [Ba7]14+, [Ba2]4+, and [Ba6]12+ are respectively replaced by the K14, KMIII , and Mସ୍୍୍ units with ୍୍୍ the same chemical valance states, resulting in K7.5Mଶ.ହ B15O30, where MIII is the

trivalent rare-earth Y3+ and Gd3+ for the derivatives K7.5Y2.5(B5O10)3 and K7.5Gd2.5(B5O10)3, respectively. While for the B-O anionic parts, the isolated [B5O10]5double rings in two series derivatives can be considered as the recombination of two [B3O6]3- single rings in β-BaB2O4 through a shared B atom. The similar structural evolution between B-O units can also be found in Ba2Mg(BO3)2 and Ba2Mg(B3O6)2.66,67 (Figure S5 in the Supporting Information) The isolated [B3O6]3units can aslo be regarded as the polymerization of three [BO3]3- units in Ba2Mg(BO3)266 through three shared O atoms in Ba2Mg(B3O6)2,67 which can also occur betweent Ba3Y(BO3)368 and Ba3Y(B3O6)3.69 Besides among borates, the structural evolution of anionic groups can also be found between different compound systems, such as, borates and phosphates (BO3→PO4),54,70 vanadates and phosphates (VO4→PO4),55 carbonates and borates (CO3→BO3),71 silicates and germanates (SiO4→GeO4),72 etc. With this, chemical cosubstitution strategy is confirmed to be a feasible strategy to design multiple compounds with diverse compositions based on the same template or maternal structures

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Figure 4. The evolution based on chemical cosubstitution strategy from β-BaB2O4 to a series of derivatives

Table 2. Bond Valence Sum, Lewis acidity value, Bond Strain Index (BSI), Global Instability Index (GII) for K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3. BVS Compounds K

M

K7CaY2(B5O10)3

0.805-1.261

K7SrY2(B5O10)3 K7BaY2(B5O10)3

Lewis acidity value (vu) II

II

Y

BSI (vu)

GII (vu)

Y

K

M

2.091

3.207

0.13-0.21

0.35

0.53

0.06

0.13

0.815-1.238

2.178

3.114

0.14-0.21

0.36

0.52

0.05

0.13

0.944-1.293

2.060

3.087

0.16-0.22

0.34

0.51

0.05

0.12

However, the relative stability of the cation-anion interactions is also indispensable for the successful synthesis of these series derivatives. All the K, MII, and Y atoms in three structures are the central of six-coordinated polyhedra, which means that the substitutable positions (Ca, Sr, and Ba) are in the similar atomic environment and can improve the feasibility of cosubstitution behaviors. The Lewis acidity values73 of K+, 13



M2+, and Y3+ are defined as the formal valence divided by the coordination number (CN = 6). And those values (Table 2) are close to each other in three related compounds, which can also ensure the feasibility of mutual substitution. Besides, the global instability index (GII) and bond strain index (BSI) values were also calculated.74-76 Generally, a BSI or GII value larger than 0.05 vu (valence unit) indicates that a structure is strained while the values larger than 0.20 vu implies that a structure is unstable.74,75 As list in Table 2, the BSI values are larger than 0.05 vu and the GII values are smaller than 0.20 vu for K7CaY2(B5O10)3 (0.06, 0.13), K7SrY2(B5O10)3 (0.05, 0.12), and K7BaY2(B5O10)3 (0.05, 0.12), indicating that they are all strained and stable. Those values are very close to each other, which is reasonable as they owns the nearly BVS values and atomic coordination environment (CN=6). 3.3 Vibrational spectroscopy and optical properties To specify and compare the coordination model of the B atoms in K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3, the infrared spectra were tested. As shown in Figure 5a, the strong bands at 1191, 1256, and 1386 cm-1 for K7CaY2(B5O10)3, 1212, 1255, and 1375 cm-1 for K7SrY2(B5O10)3, 1180, 1256, and 1378 cm-1 for K7BaY2(B5O10)3, are mainly due to the asymmetric stretching of [BO3]3- units. The strong bands at around 941 and 1027 cm-1, 941 and 1028 cm-1, 930 and 1039 cm-1 in the curves are attributed to the [BO4]5- asymmetric stretching vibrations for the Ca-, Sr-, Ba-based compounds, respectively. The absorption bands around 734 and 776 cm-1 for K7CaY2(B5O10)3, 732 and 778 cm-1 for K7SrY2(B5O10)3, 745 and 776 cm-1 for K7BaY2(B5O10)3 can be assigned to both the [BO3]3- and [BO4]5- bending modes. Based on this, the existences of the [BO3]3- triangles and the [BO4]5- tetrahedra are further confirmed, which is consistent with the results concluded from the single-crystal X-ray structural analyses and other reported-borates.77,78 Besides, the UV-vis-NIR diffuse reflectance spectra for three compounds are shown in Figure 5b. Results show that the cutoff edges of them are all lower than 190 nm, indicating that all three crystals may have potential NLO applications in the UV spectral region. 14


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Figure 5. Infrared spectra (a) and UV−vis−NIR spectra (b) of K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3.

3.4 Second-harmonic generation properties Plots of the SHG intensity versus particle sizes for ground polycrystalline samples of K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) are shown in Figure 6. Detailed features of those curves indicate that all the three crystals are type I phase-matchable based on the rule proposed by Kurtz and Perry.62 The comparison of the SHG signal produced by the K7MIIY2(B5O10)3 polycrystalline samples and the KDP samples in the same particle sizes ranging from 200 to 250 µm reveals that Ca-, Sr-, Ba-based compounds exhibit a suitable SHG response of ∼0.9, 1.1, and 1.2 × KDP, respectively. Such SHG responses are large enough for the UV NLO applications. To further investigate the NLO properties of K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba), we also calculated the second-order coefficients dij based on the first-principles calculation. The space group of K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) is R32, which belong to the class 32 point group and have only one non-vanishing independent SHG tensor component (d11) under the restriction of Kleinman symmetry. The calculated d11 are 0.65, 0.67, 0.69 pm/V for Ca-, Sr-, Ba-based compounds, respectively. The values are comparable to that of KDP (d36 = 0.39 pm/V) and also in good agreement with the experimental values and tendency (Ca < Sr < Ba), which verifies the validity of the pseudopotential methods we employed. 15



Figure 6. Powder SHG data for K7MIIY2(B5O10)3 (MII = Ca, Sr, Ba) at 1064 nm. The curves are drawn to guide the eye and are not a fit to the data.

3.5 Electronic structure calculations The characteristic features of calculated band structures for K7CaY2(B5O10)3, K7SrY2(B5O10)3, K7BaY2(B5O10)3 are plotted in Figures S6-S8 in the Supporting Information, which show a pair of bonding and antibonding orbitals separated by gaps, respectively. It is shown that all the three compounds are direct band gap crystals with the valence band (VB) maximum and the conduction band (CB) minimum located at the same Γ point. The values of band gaps were calculated to be 4.53, 4.51, and 4.47 eV for Ca-, Sr-, Ba-based crystals, respectively, and the values are smaller than that of experimental values resulting from discontinuity of exchange-correlation energy functional. These differences will be corrected using a so-called scissors energy shift when evaluated optical properties based on DFT band structure calculation results. Therefore, the scissors are adopted in the following optical properties calculations.79

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Figure 7. The partial density of states (PDOS) of K7CaY2(B5O10)3 (a), K7SrY2(B5O10)3 (b), and K7BaY2(B5O10)3 (c)

The partial density of state (PDOS) projected on the constitutional atoms of K7CaY2(B5O10)3, K7SrY2(B5O10)3, K7BaY2(B5O10)3 crystals are given in Figure 7. As can be seen from Figure 7, the VBs below the Fermi level are mainly composed of three parts in the energy range from 0 to -20 eV. (1) The higher energy subband lying between -8.5 eV and the Fermi level is dominated by O 2p orbitals with partly contributions of B 2p and Y 4d oritals. The upper two peaks of the VB between 0 and -2 eV mainly consist of O 2p orbitals with contributions of Y 4d orbitals. Likewise, the band between -2 and -8.5 eV is produced by the hybridization of B 2p, O 2p and Y 5s orbitals. (2) Besides, one narrow band with sharp peak is at about -11 eV due to almost entirely contribution of K 3p orbitals. (3) The lower parts of the VB between -16 and -20 eV are made up entirely of the B and O orbitals, especially O 2p and B 2p orbitals between -20 and -16 eV, due to strong hybridization of the B and O orbitals in the [B5O10]5- groups. The CB above the Fermi level is dominated by K 3p, B 2p, O 2p and Ca, Sr, Ba ns (n=4, 5, 6), while the bottom of CB mostly consists of K 3p and Y 4d atoms, respectively. 17



3.6 Origin of the SHG effects To further explain the donation of individual atoms in K7CaY2(B5O10)3, K7SrY2(B5O10)3, K7BaY2(B5O10)3 to the SHG effect in real space, we used SHG-density method.80 The SHG process is denoted by two virtual transition processes, namely virtual electron (VE) and virtual hole (VH) processes. The VE process contribute close to 83.2%, 84.4%, and 89.5% to the largest SHG tensors of Ca-, Sr-, Ba-based crystals, respectively, indiacting that the SHG effects of three compounds mainly come from the VE processes. Figure 8 gives a clear description that SHG-densities on the O atoms are dominant contributor in the three compounds. The [B5O10]5- group as the the basic anionic unit is composed of four [B(1,2)O3]3− and one centered [B(3)O4]5− units. From the density of the SHG effect in the [B5O10]5groups of K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3, it shows that three-coordinated [B(1)O3]3−, [B(2)O3]3− as well as the YO6 octahedra are the major sources of SHG effect, while the contributions of four-coordinated [B(3)O4]5− units and the K atoms are negligibly small in the unoccupied states of three crystals. And in occupied states, the O(1), O(2), O(3), O(4), and O(5) atoms in [B5O10]5- and YO6 groups are still the dominant contributor to SHG effect, while the K and Y atoms make a very small contribution. Based on this, we can draw the conclusion that the suitable SHG effect in the three crystals can be seen as the synergistic effects of the [B5O10]5- and YO6 basic building blocks.

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Figure 8. The SHG–density of unoccupied and occupied states of K7CaY2(B5O10)3 (a, d), K7SrY2(B5O10)3 (b, e), and K7BaY2(B5O10)3 (c, f) in the virtual-electron (VE) process.

4. Conclusion Guided by the chemical cosubstitution strategy, taking the classic β-BaB2O4 as a maternal structure, we designed and synthesized a series of noncentrosymmetric borates by simultaneously replacing the Ba2+ atoms in β-BaB2O4 for multiple rare-, alkali-, and alkaline-earth metals. Three of them, namely K7CaY2(B5O10)3, K7SrY2(B5O10)3, and K7BaY2(B5O10)3 were performed all-round characterizations by experimental and theoretical ways. Results show that they all exhibit suitable SHG responses as large as ~0.9, 1.1, 1.2 × KDP, and the UV cutoff edges are all lower than 190 nm. First-principles calculations demonstrate that the suitable SHG response originates from the cooperative effects of the [B5O10]5- and distorted [YO6]9- basic building blocks. These results confirm the feasibility of chemical cosubstitution strategy to design NLO materials and the three seclected crystals may have potential application as UV NLO materials. Supporting Information X-ray crystallographic file in CIF format; checkcif files; atomic coordinates and equivalent

isotropic

displacement

parameters,

selected

bond

lengths

for

K7MIIRE2(B5O10)3 (MII = Ca, Sr, Ba, K/RE0.5; RE = Y, Lu, Gd) and K7MIIBi2(B5O10)3 (MII = Pb, Sr); experimental powder-XRD patterns and calculated band structures for K7CaY2(B5O10)3, K7SrY2(B5O10)3, K7BaY2(B5O10)3; structural evolution from Ba2Mg(BO3)2 to Ba2Mg(B3O6)2. Those materials are available free of charge via the Internet at http://pubs.acs.org.

Accession Codes CCDC 1576439-1576450 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], 19



or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Corresponding Author *[email protected]; *[email protected]; *[email protected]

Author Contributions # These authors contributed equally.

Notes The authors declare no competing financial interest

Acknowledgment This work was financially supported by Xinjiang Key Laboratory Foundation (Grant No. 2014KL009), the National Key Research Project (Grant No. 2016YFB1102302, 2016YFB0402104), National Natural Science Foundation of China (Grant Nos. 21501194, 51425206, 51602341, 91622107), National Basic Research Program of China (Grant No. 2014CB648400), the Science and Technology Project of Urumqi (Grant No. P161010003).

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Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as

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