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Designing a Deep-Ultraviolet Nonlinear Optical Material with a Large Second Harmonic Generation Response

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† Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China
‡ Department of Chemistry, Northwestern University, Evanston Illinois 60208-3131, United States
§ Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104-2816, United States
[email protected]; [email protected]
Cite this: J. Am. Chem. Soc. 2013, 135, 11, 4215–4218
Publication Date (Web):February 28, 2013
https://doi.org/10.1021/ja400500m
Copyright © 2013 American Chemical Society
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The generation of intense coherent deep-UV light from nonlinear optical materials is crucial to applications ranging from semiconductor photolithography and laser micromachining to photochemical synthesis. However, few materials with large second harmonic generation (SHG) and a short UV-cutoff edge are effective down to 200 nm. A notable exception is KBe2BO3F2, which is obtained from a solid-state reaction of highly toxic beryllium oxide powders. We designed and synthesized a benign polar material, Ba4B11O20F, that satisfies these requirements and exhibits the largest SHG response in known borates containing neither lone-pair-active anions nor second-order Jahn–Teller-active transition metals. We developed a microscopic model to explain the enhancement, which is unexpected on the basis of conventional anionic group theory arguments. Crystal engineering of atomic displacements along the polar axis, which are difficult to attribute to or identify within unique anionic moieties, and greater cation polarizabilities are critical to the design of next-generation SHG materials.

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  85. Qi Wei, Jian-Wen Cheng, Chao He, and Guo-Yu Yang . An Acentric Calcium Borate Ca2[B5O9]·(OH)·H2O: Synthesis, Structure, and Nonliner Optical Property. Inorganic Chemistry 2014, 53 (21) , 11757-11763. https://doi.org/10.1021/ic502044d
  86. P. Shiv Halasyamani (Associate Editor). Editorial for the ACS Select Collection on Solid-State Chemistry. Inorganic Chemistry 2014, 53 (20) , 10781-10784. https://doi.org/10.1021/ic502322z
  87. Antonio Cammarata, Weiguo Zhang, P. Shiv Halasyamani, and James M. Rondinelli . Microscopic Origins of Optical Second Harmonic Generation in Noncentrosymmetric–Nonpolar Materials. Chemistry of Materials 2014, 26 (19) , 5773-5781. https://doi.org/10.1021/cm502895h
  88. Siyang Luo, Wenjiao Yao, Pifu Gong, Jiyong Yao, Zheshuai Lin, and Chuangtian Chen . Ca3Na4LiBe4B10O24F: A New Beryllium Borate with a Unique Beryl Borate ∞2[Be8B16O40F2] Layer Intrabridged by [B12O24] Groups. Inorganic Chemistry 2014, 53 (16) , 8197-8199. https://doi.org/10.1021/ic501444t
  89. Xue-Li Cao, Fang Kong, Chun-Li Hu, Xiang Xu, and Jiang-Gao Mao . Pb4V6O16(SeO3)3(H2O), Pb2VO2(SeO3)2Cl, and PbVO2(SeO3)F: New Lead(II)–Vanadium(V) Mixed-Metal Selenites Featuring Novel Anionic Skeletons. Inorganic Chemistry 2014, 53 (16) , 8816-8824. https://doi.org/10.1021/ic501548m
  90. Min Luo, GenXiang Wang, Chensheng Lin, Ning Ye, Yuqiao Zhou, and Wendan Cheng . Na4La2(CO3)5 and CsNa5Ca5(CO3)8: Two New Carbonates as UV Nonlinear Optical Materials. Inorganic Chemistry 2014, 53 (15) , 8098-8104. https://doi.org/10.1021/ic501089f
  91. Sangen Zhao, Pifu Gong, Siyang Luo, Lei Bai, Zheshuai Lin, Chengmin Ji, Tianliang Chen, Maochun Hong, and Junhua Luo . Deep-Ultraviolet Transparent Phosphates RbBa2(PO3)5 and Rb2Ba3(P2O7)2 Show Nonlinear Optical Activity from Condensation of [PO4]3– Units. Journal of the American Chemical Society 2014, 136 (24) , 8560-8563. https://doi.org/10.1021/ja504319x
  92. T. Thao Tran, P. Shiv Halasyamani, and James M. Rondinelli . Role of Acentric Displacements on the Crystal Structure and Second-Harmonic Generating Properties of RbPbCO3F and CsPbCO3F. Inorganic Chemistry 2014, 53 (12) , 6241-6251. https://doi.org/10.1021/ic500778n
  93. Min Zhang, Xin Su, Shilie Pan, Zheng Wang, Hui Zhang, Zhihua Yang, Bingbing Zhang, Lingyun Dong, Ying Wang, Fangfang Zhang, and Yun Yang . Linear and Nonlinear Optical Properties of K3B6O10Br Single Crystal: Experiment and Calculation. The Journal of Physical Chemistry C 2014, 118 (22) , 11849-11856. https://doi.org/10.1021/jp500858q
  94. Lixian Chang, Li Wang, Xin Su, Shilie Pan, Reshalaiti Hailili, Hongwei Yu, and Zhihua Yang . A Nitrate Nonlinear Optical Crystal Pb16(OH)16(NO3)16 with a Large Second-Harmonic Generation Response. Inorganic Chemistry 2014, 53 (7) , 3320-3325. https://doi.org/10.1021/ic402404a
  95. Chao Huang, Jian-Han Zhang, Chun-Li Hu, Xiang Xu, Fang Kong, and Jiang-Gao Mao . KSbB2O6 and BaSb2B4O12: Novel Boroantimonates with 3D Anionic Architectures Composed of 1D Chains of SbO6 Octahedra and B2O5 Groups. Inorganic Chemistry 2014, 53 (7) , 3847-3853. https://doi.org/10.1021/ic5001842
  96. Shujuan Han, Ying Wang, Shilie Pan, Xiaoyu Dong, Hongping Wu, Jian Han, Yun Yang, Hongwei Yu, and Chunyan Bai . Noncentrosymmetric versus Centrosymmetric: Influence of the Na+ Substitution on Structural Transition and Second-Harmonic Generation Property. Crystal Growth & Design 2014, 14 (4) , 1794-1801. https://doi.org/10.1021/cg4019103
  97. Sangen Zhao, Jia Zhang, Shu-quan Zhang, Zhihua Sun, Zheshuai Lin, Yicheng Wu, Maochun Hong, and Junhua Luo . A New UV Nonlinear Optical Material CsZn2B3O7: ZnO4 Tetrahedra Double the Efficiency of Second-Harmonic Generation. Inorganic Chemistry 2014, 53 (5) , 2521-2527. https://doi.org/10.1021/ic402667m
  98. Anqing Jiao, Hongwei Yu, Hongping Wu, Shilie Pan, and Xingwen Zhang . A New Cesium Pentaborate with New B10O19 Building Blocks. Inorganic Chemistry 2014, 53 (5) , 2358-2360. https://doi.org/10.1021/ic403070b
  99. Shichao Wang, Ning Ye, and Guohong Zou . Three New Alkaline Beryllium Borates LiBeBO3, Li6Be3B4O12, and Li8Be5B6O18 in the Ternary Phase Diagrams Li2O–BeO–B2O3. Inorganic Chemistry 2014, 53 (5) , 2742-2748. https://doi.org/10.1021/ic5000843
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  107. Yu-Cheng Hao, Chun-Li Hu, Xiang Xu, Fang Kong, and Jiang-Gao Mao . SrGe2B2O8 and Sr3Ge2B6O16: Novel Strontium Borogermanates with Three-Dimensional and Layered Anionic Architectures. Inorganic Chemistry 2013, 52 (23) , 13644-13650. https://doi.org/10.1021/ic402214p
  108. Lingyun Dong, Shilie Pan, Ying Wang, Hongwei Yu, Xiaoyu Dong, Shujuan Han, and Min Zhang . Special ∞1[OPb2] Chains and ∞1[O2Pb3] Ribbons Based on OPb4 Anion-Centered Tetrahedra in Pb2(O4Pb8)(BO3)3Br3 and Pb2(O8Pb12)(BO3)2Br6. Inorganic Chemistry 2013, 52 (19) , 11377-11384. https://doi.org/10.1021/ic401655h
  109. Hongwei Yu, Shilie Pan, Hongping Wu, Zhihua Yang, Lingyun Dong, Xin Su, Bingbing Zhang, and Hongyi Li . Effect of Rigid Units on the Symmetry of the Framework: Design and Synthesis of Centrosymmetric NaBa4(B5O9)2F2Cl and Noncentrosymmetric NaBa4(AlB4O9)2Br3. Crystal Growth & Design 2013, 13 (8) , 3514-3521. https://doi.org/10.1021/cg4004774
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  119. Minqiang Gai, Ying Wang, Tinghao Tong, Liying Wang, Zhihua Yang, Xin Zhou, Shilie Pan. Ba(B 2 OF 3 (OH) 2 ) 2 with well-ordered OH/F anions and a unique B 2 OF 3 (OH) 2 dimer. Chemical Communications 2020, 56 (22) , 3301-3304. https://doi.org/10.1039/C9CC06532F
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  230. T.B. Bekker, V.N. Vedenyapin, A.G. Khamoyan. Birefringence of the new fluoride borates Ba 2 Na 3 [B 3 O 6 ] 2 F and Ba 7 (BO 3 ) 4−y F 2+3y in the Na, Ba, B//O, F quaternary reciprocal system. Materials Research Bulletin 2017, 91 , 54-58. https://doi.org/10.1016/j.materresbull.2017.03.024
  231. Kaweri Gambhir, Bhumika Ray, Ranjana Mehrotra, Parag Sharma. Morphology dependent two photon absorption in plasmonic structures and plasmonic–organic hybrids. Optics & Laser Technology 2017, 90 , 201-210. https://doi.org/10.1016/j.optlastec.2016.12.003
  232. Lingyun Dong, Jiao Yang, Shigang Shen, Zhenzhen Liu, Xiaojing Chen, Sufang Sun. [O 2 Pb 3 ] 2 (BO 3 )Br: An Oxidoborate Oxide Bromide with the ∞1 [O 2 Pb 3 ] Double Chains Based on Edge-sharing OPb 4 Tetrahedra. Zeitschrift für anorganische und allgemeine Chemie 2017, 643 (7) , 471-476. https://doi.org/10.1002/zaac.201600416
  233. Kui Wu, Shilie Pan. Li2HgMS4 (M = Si, Ge, Sn): New Quaternary Diamond-Like Semiconductors for Infrared Laser Frequency Conversion. Crystals 2017, 7 (4) , 107. https://doi.org/10.3390/cryst7040107
  234. T. Thao Tran, Nathan Z. Koocher, James M. Rondinelli, P. Shiv Halasyamani. Beryllium-Free β-Rb 2 Al 2 B 2 O 7 as a Possible Deep-Ultraviolet Nonlinear Optical Material Replacement for KBe 2 BO 3 F 2. Angewandte Chemie 2017, 129 (11) , 3015-3019. https://doi.org/10.1002/ange.201612236
  235. T. Thao Tran, Nathan Z. Koocher, James M. Rondinelli, P. Shiv Halasyamani. Beryllium-Free β-Rb 2 Al 2 B 2 O 7 as a Possible Deep-Ultraviolet Nonlinear Optical Material Replacement for KBe 2 BO 3 F 2. Angewandte Chemie International Edition 2017, 56 (11) , 2969-2973. https://doi.org/10.1002/anie.201612236
  236. Fei-Fei Mao, Chun-Li Hu, Xiang Xu, Dong Yan, Bing-Ping Yang, Jiang-Gao Mao. Bi(IO 3 )F 2 : The First Metal Iodate Fluoride with a Very Strong Second Harmonic Generation Effect. Angewandte Chemie 2017, 129 (8) , 2183-2187. https://doi.org/10.1002/ange.201611770
  237. Fei-Fei Mao, Chun-Li Hu, Xiang Xu, Dong Yan, Bing-Ping Yang, Jiang-Gao Mao. Bi(IO 3 )F 2 : The First Metal Iodate Fluoride with a Very Strong Second Harmonic Generation Effect. Angewandte Chemie International Edition 2017, 56 (8) , 2151-2155. https://doi.org/10.1002/anie.201611770
  238. Sangen Zhao, Yi Yang, Yaoguo Shen, Bingqing Zhao, Lina Li, Chengmin Ji, Zhenyue Wu, Daqiang Yuan, Zheshuai Lin, Maochun Hong, Junhua Luo. Cooperation of Three Chromophores Generates the Water-Resistant Nitrate Nonlinear Optical Material Bi 3 TeO 6 OH(NO 3 ) 2. Angewandte Chemie 2017, 129 (2) , 555-559. https://doi.org/10.1002/ange.201609876
  239. Sangen Zhao, Yi Yang, Yaoguo Shen, Bingqing Zhao, Lina Li, Chengmin Ji, Zhenyue Wu, Daqiang Yuan, Zheshuai Lin, Maochun Hong, Junhua Luo. Cooperation of Three Chromophores Generates the Water-Resistant Nitrate Nonlinear Optical Material Bi 3 TeO 6 OH(NO 3 ) 2. Angewandte Chemie International Edition 2017, 56 (2) , 540-544. https://doi.org/10.1002/anie.201609876
  240. Maierhaba Abudoureheman, Shujuan Han, Xiaoyu Dong, Bing-Hua Lei, Ying Wang, Zhihua Yang, Xifa Long, Shilie Pan. Syntheses, characterization and theoretical studies of three apatite-type phosphates MPb4(PO4)3 (M = K, Rb, Cs). Journal of Alloys and Compounds 2017, 690 , 330-336. https://doi.org/10.1016/j.jallcom.2016.08.115
  241. Zhaohui Chen, Yaqin Liu, Yunjing Shi, Wenyao Zhang, Qun Jing, Yuan Fang, Xiaoyu Dong. M 3 V 2 B 10 O 23 (M = Ca, Sr): two new vanadoborates with [V 2 B 10 O 23 ] ∞ double layers. New Journal of Chemistry 2017, 41 (14) , 6730-6735. https://doi.org/10.1039/C6NJ04069A
  242. Miriding Mutailipu, Xin Su, Min Zhang, Zhihua Yang, Shilie Pan. Ba n+2 Zn n (BO 3 ) n (B 2 O 5 )F n (n = 1, 2): new members of the zincoborate fluoride series with two kinds of isolated B–O units. Inorganic Chemistry Frontiers 2017, 4 (2) , 281-288. https://doi.org/10.1039/C6QI00467A
  243. Lin Li, Ying Wang, Bing-Hua Lei, Shujuan Han, Zhihua Yang, Hongyi Li, Shilie Pan. LiRb 2 PO 4 : a new deep-ultraviolet nonlinear optical phosphate with a large SHG response. Journal of Materials Chemistry C 2017, 5 (2) , 269-274. https://doi.org/10.1039/C6TC04565K
  244. Guang-mao Li, Qiong Liu, Kui Wu, Zhi-hua Yang, Shi-lie Pan. Na 2 CdGe 2 Q 6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses. Dalton Transactions 2017, 46 (9) , 2778-2784. https://doi.org/10.1039/C7DT00087A
  245. Ming Wen, Hongping Wu, Xin Su, Juanjuan Lu, Zhihua Yang, Xiaohong Wu, Shilie Pan. ACaBO 3 (A = Cs, Rb): two new cubic borates with isolated BO 3 groups. Dalton Transactions 2017, 46 (15) , 4968-4974. https://doi.org/10.1039/C7DT00251C
  246. Qi Wei, Li Sun, Jie Zhang, Guo-Yu Yang. Two deep-ultraviolet nonlinear optical alkaline-earth metal borates based on different types of oxoboron clusters. Dalton Transactions 2017, 46 (24) , 7911-7916. https://doi.org/10.1039/C7DT01677H
  247. Guangmao Li, Ni Zhen, Yu Chu, Zhongxiang Zhou. Li 3 Ge 3 Se 6 : the first ternary lithium germanium selenide with interesting ∞ [Ge 6 Se 12 ] n chains constructed by ethane-like [Ge 2 Se 6 ] 6− clusters. Dalton Transactions 2017, 46 (47) , 16399-16403. https://doi.org/10.1039/C7DT03781C
  248. Lingyun Dong, Liangliang Jia, Lijun Wang. New lead( ii ) borates in the PbO/PbF 2 /H 3 BO 3 ternary phase diagram: syntheses and structures of β-Pb 6 B 10 O 21 and Pb 4 B 8 O 16. New Journal of Chemistry 2017, 41 (11) , 4291-4294. https://doi.org/10.1039/C7NJ00203C
  249. Juanjuan Lu, Guoqiang Shi, Hongping Wu, Ming Wen, Dianwei Hou, Zhihua Yang, Fangfang Zhang, Shilie Pan. Experimental and ab initio studies of two UV nonlinear optical materials. RSC Advances 2017, 7 (33) , 20259-20265. https://doi.org/10.1039/C7RA02027A
  250. Leyan Nian, Junben Huang, Kui Wu, Zhi Su, Zhihua Yang, Shilie Pan. BaCu 2 M IV Q 4 (M IV = Si, Ge, and Sn; Q = S, Se): synthesis, crystal structures, optical performances and theoretical calculations. RSC Advances 2017, 7 (47) , 29378-29385. https://doi.org/10.1039/C7RA05022D
  251. Ying Wang, Shilie Pan. Recent development of metal borate halides: Crystal chemistry and application in second-order NLO materials. Coordination Chemistry Reviews 2016, 323 , 15-35. https://doi.org/10.1016/j.ccr.2015.12.008
  252. Feng Sun, Li Wang, Constantinos C. Stoumpos. Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb2O[BO2(OH)] based on anion-centered OPb4 tetrahedra. Journal of Solid State Chemistry 2016, 240 , 61-66. https://doi.org/10.1016/j.jssc.2016.05.018
  253. Qi Wei, Jia-Jia Wang, Chao He, Jian-Wen Cheng, Guo-Yu Yang. Deep-Ultraviolet Nonlinear Optics in a Borate Framework with 21-Ring Channels. Chemistry - A European Journal 2016, 22 (31) , 10759-10762. https://doi.org/10.1002/chem.201602135
  254. Pai Shan, Tongqing Sun, Hong Chen, Hongde Liu, Shaolin Chen, Xuanwen Liu, Yongfa Kong, Jingjun Xu. Crystal growth and optical characteristics of beryllium-free polyphosphate, KLa(PO3)4, a possible deep-ultraviolet nonlinear optical crystal. Scientific Reports 2016, 6 (1) https://doi.org/10.1038/srep25201
  255. O.V. Bovgyra, V.Y. Kurlak, M. Chrunik, A. Majchrowski, L.R. Jaroszewicz, K. Ozga. Anisotropy of inter-band transitions and band structure of Cs3Zn6B9O21 nonlinear optical crystals. Optical Materials 2016, 56 , 129-133. https://doi.org/10.1016/j.optmat.2015.12.022
  256. Zhi Li, Qiong Liu, Shujuan Han, Toshiaki Iitaka, Haibin Su, Takami Tohyama, Huaidong Jiang, Yongjun Dong, Bin Yang, Fangfang Zhang, Zhihua Yang, Shilie Pan. Nonlinear electronic polarization and optical response in borophosphate BPO4. Physical Review B 2016, 93 (24) https://doi.org/10.1103/PhysRevB.93.245125
  257. Weiguo Zhang, Hongwei Yu, Hongping Wu, P. Halasyamani. Crystal Growth and Associated Properties of a Nonlinear Optical Crystal—Ba2Zn(BO3)2. Crystals 2016, 6 (6) , 68. https://doi.org/10.3390/cryst6060068
  258. Jianhua Gao, Xi Liu, Limei Song, Xunshan Sha, Pan Zhao, Ping Guo. Synthesis and structure of a new halophosphate Sr 3 P 3 O 10 Cl with the flexible [P 3 O 10 ] 5− anions. Solid State Sciences 2016, 55 , 159-163. https://doi.org/10.1016/j.solidstatesciences.2016.03.008
  259. Guohong Zou, Chensheng Lin, Hyung Kim, Hongil Jo, Kang Ok. Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response. Crystals 2016, 6 (4) , 42. https://doi.org/10.3390/cryst6040042
  260. Tian-Jiao Zhang, Rui Pan, Huan He, Bai-Feng Yang, Guo-Yu Yang. Solvothermal Synthesis and Structure of Two New Borates Containing [B7O9(OH)5]2− and [B12O18(OH)6]6− Clusters. Journal of Cluster Science 2016, 27 (2) , 625-633. https://doi.org/10.1007/s10876-015-0962-y
  261. Qiong Zhang, Xiaohe Tian, Zhangjun Hu, Caroline Brommesson, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Zhaoqi Sun, Yupeng Tian, Kajsa Uvdal. Nonlinear optical response and two-photon biological applications of a new family of imidazole-pyrimidine derivatives. Dyes and Pigments 2016, 126 , 286-295. https://doi.org/10.1016/j.dyepig.2015.11.026
  262. Xiaopeng Zhang, Linhua Zhu, Xianghui Wang, Zaifeng Shi, Qiang Lin. Mechano-induced multi-functional optical switches based on chiral cyclometalated platinum(II) complexes. Inorganica Chimica Acta 2016, 442 , 56-63. https://doi.org/10.1016/j.ica.2015.11.028
  263. S. Pan, Y. Wang, K.R. Poeppelmeier. Frequency-Doubling Oxide Fluorides, Borate Fluorides, and Fluorooxoborates. 2016,,, 311-354. https://doi.org/10.1016/B978-0-12-801639-8.00015-5
  264. Xinglong Chen, Fangfang Zhang, Lili Liu, Bing-Hua Lei, Xiaoyu Dong, Zhihua Yang, Hongyi Li, Shilie Pan. Li 3 AlSiO 5 : the first aluminosilicate as a potential deep-ultraviolet nonlinear optical crystal with the quaternary diamond-like structure. Physical Chemistry Chemical Physics 2016, 18 (6) , 4362-4369. https://doi.org/10.1039/C5CP06884C
  265. Linping Li, Zhihua Yang, Bing-Hua Lei, Qingrong Kong, Ming-Hsein Lee, Bingbing Zhang, Shilie Pan, Jun Zhang. Active performance of tetrahedral groups to SHG response: theoretical interpretations of Ge/Si-containing borate crystals. Physical Chemistry Chemical Physics 2016, 18 (8) , 6077-6084. https://doi.org/10.1039/C5CP07313H
  266. Lin Li, Shujuan Han, Bing-Hua Lei, Ying Wang, Hongyi Li, Zhihua Yang, Shilie Pan. Three new phosphates with isolated P 2 O 7 units: noncentrosymmetric Cs 2 Ba 3 (P 2 O 7 ) 2 and centrosymmetric Cs 2 BaP 2 O 7 and LiCsBaP 2 O 7. Dalton Transactions 2016, 45 (9) , 3936-3942. https://doi.org/10.1039/C5DT05026J
  267. Xiangyu Zhang, Danni Li, Hongping Wu, Zhihua Yang, Shilie Pan. M 2 Ca 3 B 16 O 28 (M = Rb, Cs): structures analogous to SBBO with three-dimensional open-framework layers. RSC Advances 2016, 6 (17) , 14205-14210. https://doi.org/10.1039/C5RA21011A
  268. A. H. Reshak, Sushil Auluck. Influence of an oxygen vacancy on the electronic structure of the asymmetric mixed borate–carbonate Pb 7 O(OH) 3 (CO 3 ) 3 (BO 3 ). RSC Advances 2016, 6 (23) , 18965-18972. https://doi.org/10.1039/C5RA24601F
  269. Jun Li, Zuju Ma, Chao He, Qiaohong Li, Kechen Wu. An effective strategy to achieve deeper coherent light for LiB 3 O 5. Journal of Materials Chemistry C 2016, 4 (10) , 1926-1934. https://doi.org/10.1039/C5TC03814F
  270. Guopeng Han, Qiong Liu, Ying Wang, Xin Su, Zhihua Yang, Shilie Pan. Experimental and theoretical studies on the linear and nonlinear optical properties of lead phosphate crystals LiPbPO 4. Physical Chemistry Chemical Physics 2016, 18 (28) , 19123-19129. https://doi.org/10.1039/C6CP02672A
  271. Li-Jun Zhang, Yan-Yan Li, Peng-Fei Liu, Ling Chen. Li 3 Cs 2 M 2 B 3 P 6 O 24 (M = Pb, Sr): borophosphates with double six-membered ring of [BP 2 O 8 ] 3−. Dalton Trans. 2016, 45 (16) , 7124-7130. https://doi.org/10.1039/C6DT00498A
  272. Yun Yang, Xiaoyu Dong, Shilie Pan. New fluoroborate Cd 8 B 5 O 15 F with two different isolated borate anions prepared by an open high-temperature solution method. Dalton Transactions 2016, 45 (16) , 7008-7013. https://doi.org/10.1039/C6DT00621C
  273. Ni Zhen, Kui Wu, Ying Wang, Qiang Li, Wenhui Gao, Dianwei Hou, Zhihua Yang, Huaidong Jiang, Yongjun Dong, Shilie Pan. BaCdSnS 4 and Ba 3 CdSn 2 S 8 : syntheses, structures, and non-linear optical and photoluminescence properties. Dalton Transactions 2016, 45 (26) , 10681-10688. https://doi.org/10.1039/C6DT01537A
  274. Xuefei Wang, Fangfang Zhang, Bing-Hua Lei, Zhihua Yang, Shilie Pan. Nonlinear optical response mechanism of noncentrosymmetric lead borate Pb 6 [B 4 O 7 (OH) 2 ] 3 with three crystallographically independent [B 4 O 7 (OH) 2 ] 4− chains. RSC Advances 2016, 6 (103) , 100849-100856. https://doi.org/10.1039/C6RA23193D
  275. Xinping Ge, Xiaoping Gan, Shun Yao, Kang Wang, Weiju Zhu, Jianhua Yu, Jieying Wu, Yupeng Tian, Hongping Zhou. Rationally designed two-photon absorption compounds based on benzoxazole derivatives: structure–property relationships and bio-imaging applications. Journal of Materials Chemistry B 2016, 4 (16) , 2785-2793. https://doi.org/10.1039/C6TB00201C
  276. Bing-Hua Lei, Qingrong Kong, Zhihua Yang, Yun Yang, Ying Wang, Shilie Pan. Hierarchized band gap and enhanced optical responses of trivalent rare-earth metal nitrates due to (d–p)π conjugation interactions. Journal of Materials Chemistry C 2016, 4 (26) , 6295-6301. https://doi.org/10.1039/C6TC01512C
  277. Maierhaba Abudoureheman, Shujuan Han, Bing-Hua Lei, Zhihua Yang, Xifa Long, Shilie Pan. KPb 2 (PO 3 ) 5 : a novel nonlinear optical lead polyphosphate with a short deep-UV cutoff edge. Journal of Materials Chemistry C 2016, 4 (45) , 10630-10637. https://doi.org/10.1039/C6TC03424A
  278. Guang Huang, Rui Pan, Huan He, Bai-Feng Yang, Guo-Yu Yang. Two Borate Supramolecular Frameworks Based on B4O5(OH)4 Cluster Units. Journal of Cluster Science 2015, 26 (6) , 1993-2003. https://doi.org/10.1007/s10876-015-0894-6
  279. Guang Huang, Rui Pan, Huan He, Bai-Feng Yang, Guo-Yu Yang. Two New Borates Made of [B5O6(OH)4]− and [B5O10(OH)]6− Clusters, Accompanying a Novel In Situ Organic Reaction. Journal of Cluster Science 2015, 26 (6) , 2023-2032. https://doi.org/10.1007/s10876-015-0900-z
  280. Jun-Ling Song, Chun-Li Hu, Xiang Xu, Fang Kong, Jiang-Gao Mao. Synthesis, crystal structures and properties of lead phosphite compounds. Journal of Solid State Chemistry 2015, 231 , 198-203. https://doi.org/10.1016/j.jssc.2015.08.031
  281. Yuan Liu, Rui Pan, Jian-Wen Cheng, Huan He, Bai-Feng Yang, Qiang Zhang, Guo-Yu Yang. A Series of Aluminoborates Templated or Supported by Zinc-Amine Complexes. Chemistry - A European Journal 2015, 21 (44) , 15732-15739. https://doi.org/10.1002/chem.201501420
  282. Hongping Wu, Hongwei Yu, Zhihua Yang, Jian Han, Kui Wu, Shilie Pan. Linear optical and thermo-physical properties of polar K3B6O10Cl crystal. Journal of Materiomics 2015, 1 (3) , 221-228. https://doi.org/10.1016/j.jmat.2015.06.001
  283. Donghai An, Min Zhang, Danni Li, Shilie Pan, Huimin Chen, Zhihua Yang, Yingtao Zhu, Yi Sun, Hui Zhang, Yangyang Li. Linear and nonlinear optical properties of aluminum borate crystal Al 5 BO 9 : Experiment and calculation. Journal of Materials Research 2015, 30 (15) , 2319-2326. https://doi.org/10.1557/jmr.2015.204
  284. Lili Liu, Yun Yang, Xiaoyu Dong, Chen Lei, Shujuan Han, Shilie Pan. Ba 2 B 6 O 11 , a Member of the BaO-B 2 O 3 Family, Featuring a Layer Framework. European Journal of Inorganic Chemistry 2015, 2015 (20) , 3328-3335. https://doi.org/10.1002/ejic.201500399
  285. Xi Du, Hang Zhang, Shifeng Zhou, Fangteng Zhang, Guoping Dong, Jianrong Qiu. Femtosecond laser induced space-selective precipitation of a deep-ultraviolet nonlinear BaAlBO3F2 crystal in glass. Journal of Non-Crystalline Solids 2015, 420 , 17-20. https://doi.org/10.1016/j.jnoncrysol.2014.12.023
  286. A.G. Tyulyupa, V.V. Voronov, P.P. Fedorov. Polymorphism of lead oxoborate. Thermochimica Acta 2015, 612 , 34-39. https://doi.org/10.1016/j.tca.2015.05.010
  287. James M. Rondinelli, Emmanouil Kioupakis. Predicting and Designing Optical Properties of Inorganic Materials. Annual Review of Materials Research 2015, 45 (1) , 491-518. https://doi.org/10.1146/annurev-matsci-070214-021150
  288. Qun Jing, Xiaoyu Dong, Xinglong Chen, Zhihua Yang, Shilie Pan, Chen Lei. The lone-pairs enhanced birefringence and SHG response: A DFT investigation on M2B5O9Cl (M=Sr, Ba, and Pb). Chemical Physics 2015, 453-454 , 42-46. https://doi.org/10.1016/j.chemphys.2015.04.001
  289. Chun-Li Hu, Jiang-Gao Mao. Recent advances on second-order NLO materials based on metal iodates. Coordination Chemistry Reviews 2015, 288 , 1-17. https://doi.org/10.1016/j.ccr.2015.01.005
  290. Jun-Ling Song, Chun-Li Hu, Xiang Xu, Fang Kong, Jiang-Gao Mao. A Facile Synthetic Route to a New SHG Material with Two Types of Parallel π-Conjugated Planar Triangular Units. Angewandte Chemie 2015, 127 (12) , 3750-3753. https://doi.org/10.1002/ange.201412344
  291. Jun-Ling Song, Chun-Li Hu, Xiang Xu, Fang Kong, Jiang-Gao Mao. A Facile Synthetic Route to a New SHG Material with Two Types of Parallel π-Conjugated Planar Triangular Units. Angewandte Chemie International Edition 2015, 54 (12) , 3679-3682. https://doi.org/10.1002/anie.201412344
  292. Zhihua Yang, Xuchu Huang, Qiong Liu, Dianwei Hou, Bingbing Zhang, Shengshi Huang, Shilie Pan, Yun Yang, Min Zhang. Cation effect investigation on electronic structure, magnetic and optical properties of Li2Pb2CuB4O10. Chemical Physics 2015, 447 , 60-63. https://doi.org/10.1016/j.chemphys.2014.12.001
  293. Xiaoshan Wang, Lijuan Liu, Xiaoyang Wang, Lei Bai, Chuangtian Chen. Growth and optical properties of the novel nonlinear optical crystal NaSr 3 Be 3 B 3 O 9 F 4. CrystEngComm 2015, 17 (4) , 925-929. https://doi.org/10.1039/C4CE02096K
  294. Xin Su, Zhihua Yang, Ming-Hsien Lee, Shilie Pan, Ying Wang, Xiaoyun Fan, Zhenjun Huang, Bingbing Zhang. Evidence of “new hot spots” from determining the nonlinear optical behavior of materials: mechanistic studies of the vanadium borate crystal, Na 3 VO 2 B 6 O 11. Physical Chemistry Chemical Physics 2015, 17 (7) , 5338-5344. https://doi.org/10.1039/C4CP04248D
  295. Lei Geng, Changyu Meng, Hongyan Lu, Zhongzhen Luo, Chensheng Lin, Wendan Cheng. Bi 2 Te(IO 3 )O 5 Cl: a novel polar iodate oxychloride exhibiting a second-order nonlinear optical response. Dalton Transactions 2015, 44 (5) , 2469-2475. https://doi.org/10.1039/C4DT03532A
  296. Yeong Hun Kim, T. Thao Tran, P. Shiv Halasyamani, Kang Min Ok. Macroscopic polarity control with alkali metal cation size and coordination environment in a series of tin iodates. Inorganic Chemistry Frontiers 2015, 2 (4) , 361-368. https://doi.org/10.1039/C4QI00243A
  297. Bing-Hua Lei, Qun Jing, Zhihua Yang, Bingbing Zhang, Shilie Pan. Anomalous second-harmonic generation response in SrBPO 5 and BaBPO 5. Journal of Materials Chemistry C 2015, 3 (7) , 1557-1566. https://doi.org/10.1039/C4TC02443E
  298. Jun-Ling Song, Xiang Xu, Chun-Li Hu, Fang Kong, Jiang-Gao Mao. A facile strategy to adjust the density of planar triangle units in lead borate–nitrates. CrystEngComm 2015, 17 (21) , 3953-3960. https://doi.org/10.1039/C5CE00509D
  299. Fangyuan Zhang, Fangfang Zhang, Jing Qun, Shilie Pan, Zhihua Yang, Dianzeng Jia. Synthesis, characterization and theoretical studies of nonlinear optical crystal Sr 2 B 5 O 9 (OH)·H 2 O. Physical Chemistry Chemical Physics 2015, 17 (16) , 10489-10496. https://doi.org/10.1039/C5CP00864F
  300. Yun Yang, Xin Su, Shilie Pan, Zhihua Yang. Effect of cation substitution on structural transition: synthesis, characterization and theoretical studies of NaCa 4 B 3 O 9 , NaCaBO 3 , NaSrBO 3 and Li 4 CaB 2 O 6. Physical Chemistry Chemical Physics 2015, 17 (39) , 26359-26368. https://doi.org/10.1039/C5CP04420K
  301. Lu Liu, Bingbing Zhang, Fangfang Zhang, Shilie Pan, Fangyuan Zhang, Xingwen Zhang, Xiaoyu Dong, Zhihua Yang. Pb 6 Ba 2 (BO 3 ) 5 X (X = Cl, Br): new borate halides with strong predicted optical anisotropies derived from Pb 2+ and (BO 3 ) 3−. Dalton Transactions 2015, 44 (15) , 7041-7047. https://doi.org/10.1039/C5DT00641D
  302. Ming Wen, Zhipeng Lian, Hongping Wu, Xin Su, Qingfeng Yan, Juanjuan Lu, Zhihua Yang, Shilie Pan. Ba 7 (BO 3 ) 3 GeO 4 X (X = Cl, Br): borogermanate halides with rigid GeO 4 tetrahedra and flexible XBa 6 octahedra. RSC Advances 2015, 5 (66) , 53448-53454. https://doi.org/10.1039/C5RA07450A
  303. Qiong Zhang, Xiaohe Tian, Zhangjun Hu, Caroline Brommesson, Jieying Wu, Hongping Zhou, Shengli Li, Jiaxiang Yang, Zhaoqi Sun, Yupeng Tian, Kajsa Uvdal. A series of Zn( ii ) terpyridine complexes with enhanced two-photon-excited fluorescence for in vitro and in vivo bioimaging. Journal of Materials Chemistry B 2015, 3 (36) , 7213-7221. https://doi.org/10.1039/C5TB01185J
  304. Lei Geng, Qiang Li, Chang-Yu Meng, Kai Dai, Hong-Yan Lu, Chen-Sheng Lin, Wen-Dan Cheng. BaBi(SeO 3 ) 2 Cl: a new polar material showing high second-harmonic generation efficiency enhanced by constructive alignment of chloride ions. Journal of Materials Chemistry C 2015, 3 (47) , 12290-12296. https://doi.org/10.1039/C5TC02925B
  305. Hongyi Li, Lingyun Dong, Yi Lu, Shilie Pan, Xiaoquan Lu, Hongwei Yu, Hongping Wu, Xin Su, Zhihua Yang. Synthesis, crystal structure, and optical properties of a new lead barium borate, PbBa 2 (B 3 O 6 ) 2. Journal of Alloys and Compounds 2014, 615 , 561-565. https://doi.org/10.1016/j.jallcom.2014.06.187
  306. Qun Jing, Xiaoyu Dong, Zhihua Yang, Shilie Pan, Bingbing Zhang, Xuchu Huang, Mingwei Chen. The interaction between cations and anionic groups inducing SHG enhancement in a series of apatite-like crystals: A first-principles study. Journal of Solid State Chemistry 2014, 219 , 138-142. https://doi.org/10.1016/j.jssc.2014.07.027
  307. Jie Chen, Min Luo, Ning Ye. Syntheses, characterization and nonlinear optical properties of sodium–scandium carbonate Na 5 Sc(CO 3 ) 4 ·2H 2 O. Solid State Sciences 2014, 36 , 24-28. https://doi.org/10.1016/j.solidstatesciences.2014.07.001
  308. Emre Tasci, Alessandro Stroppa, Domenico Di Sante, Gianluca Giovannetti, Silvia Picozzi, J Perez-Mato. The “How-to” Guide to Computational Crystallography. 2014,,, 449-488. https://doi.org/10.1201/b17412-12
  309. Jun-Hua Wang, Jian-Wen Cheng, Qi Wei, Huan He, Bai-Feng Yang, Guo-Yu Yang. NaB 3 O 5 ·0.5H 2 O and NH 4 NaB 6 O 10 : Two Cluster Open Frameworks with Chiral Quartz and Achiral Primitive Cubic Nets Constructed from Oxo Boron Cluster Building Units. European Journal of Inorganic Chemistry 2014, 2014 (25) , 4079-4083. https://doi.org/10.1002/ejic.201402318
  310. Qin Meng, Guo-Ming Wang, Huan He, Bai-Feng Yang, Guo-Yu Yang. Syntheses and Crystal Structures of Two New Pentaborates Templated by Transition-Metal Complexes. Journal of Cluster Science 2014, 25 (5) , 1295-1305. https://doi.org/10.1007/s10876-014-0707-3
  311. Qin Meng, Guo-Ming Wang, Jing Xue, Bai-Feng Yang, Huan He, Guo-Yu Yang. Synthesis, Structural Characterization and Properties of Two Strontium Borates Constructed from Oxo Boron Clusters. Journal of Cluster Science 2014, 25 (5) , 1319-1329. https://doi.org/10.1007/s10876-014-0710-8
  312. Sangen Zhao, Pifu Gong, Lei Bai, Xiang Xu, Shuquan Zhang, Zhihua Sun, Zheshuai Lin, Maochun Hong, Chuangtian Chen, Junhua Luo. Beryllium-free Li4Sr(BO3)2 for deep-ultraviolet nonlinear optical applications. Nature Communications 2014, 5 (1) https://doi.org/10.1038/ncomms5019
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  325. Hongwei Yu, Hongping Wu, Shilie Pan, Bingbing Zhang, Lingyun Dong, Shujuan Han, Zhihua Yang. Pb 4 Zn 2 B 10 O 21 : a congruently melting lead zinc borate with a novel [B 10 O 24 ] anionic group and an interesting [Pb 4 O 12 ] ∞ chain. New J. Chem. 2014, 38 (1) , 285-291. https://doi.org/10.1039/C3NJ00893B
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  330. Yu-Cheng Hao, Xiang Xu, Fang Kong, Jun-Ling Song, Jiang-Gao Mao. PbCd 2 B 6 O 12 and EuZnB 5 O 10 : syntheses, crystal structures and characterizations of two new mixed metal borates. CrystEngComm 2014, 16 (33) , 7689. https://doi.org/10.1039/C4CE00777H
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