Inch-sized K[NH2(CH2COO)2]: a High-Performance UV Nonlinear Optical Crystal Enabled by Novel Flexible π-Conjugated Building Units, [NH2(CH2COO)2]−
Yujie Fan
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorLingli Wu
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorChensheng Lin
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorHaotian Tian
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorChao Wang
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorTao Yan
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorCorresponding Author
Min Luo
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
E-mail: [email protected]
Search for more papers by this authorYujie Fan
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorLingli Wu
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorChensheng Lin
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorHaotian Tian
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorChao Wang
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorTao Yan
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Search for more papers by this authorCorresponding Author
Min Luo
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian, 350002 China
E-mail: [email protected]
Search for more papers by this authorAbstract
High-performance ultraviolet (UV) nonlinear optical (NLO) crystals must exhibit three critical properties: a large second-harmonic generation (SHG) response, adequate birefringence, and a short UV cutoff edge. However, these key characteristics are often interdependent and challenging to achieve simultaneously within a single crystal. In this study, a novel non-centrosymmetric compound, K[NH2(CH2COO)2] is introduced, synthesized from the innovative flexible π-conjugated group [NH2(CH2COO)2]−. Benefiting from the excellent microscopic optical properties of the flexible π-conjugated [NH2(CH2COO)2]− groups, despite the suboptimal arrangement of groups within the compound, K[NH2(CH2COO)2] still demonstrates a remarkable balance in its linear and nonlinear optical performance. This includes a strong SHG response of 3 times that of KDP, suitable birefringence of 0.088@1064 nm, and a short UV cutoff edge at 208 nm. Emphatically, high-quality, inch-sized single crystals (up to 60 × 46 × 30 mm3) are successfully grown using a water solution technique, paving the way for practical applications of this promising material.
Conflict of Interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
Supporting Information
| Filename | Description |
|---|---|
| lpor202500105-sup-0001-SuppMat.docx3.7 MB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1S. Zhao, J. Zhang, S. Zhang, Z. Sun, Z. Lin, Y. Wu, M. Hong, J. Luo, Inorg. Chem. 2014, 53, 2521.
- 2T. Sasaki, Y. Mori, M. Yoshimura, Y. K. Yap, T. Kamimura, Mater. Sci. Eng.: R: Rep. 2000, 30, 1.
- 3Z. Xia, K. R. Poeppelmeier, Acc. Chem. Res. 2017, 50, 1222.
- 4K. M. Ok, Acc. Chem. Res. 2016, 49, 2774.
- 5Y. Pan, S.-P. Guo, B.-W. Liu, H.-G. Xue, G.-C. Guo, Coord. Chem. Rev. 2018, 374, 464.
- 6P. S. Halasyamani, J. M. Rondinelli, Nat. Commun. 2018, 9, 2972.
- 7T. T. Tran, H. Yu, J. M. Rondinelli, K. R. Poeppelmeier, P. S. Halasyamani, Chem. Mater. 2016, 28, 5238.
- 8Z. Yan, J. Fan, S. Pan, M. Zhang, Chem. Soc. Rev. 2024, 53, 6568.
- 9W. Zhang, X. Hou, S. Han, S. Pan, Coord. Chem. Rev. 2024, 505, 215664.
- 10F. Hou, D. Mei, M. Xia, Y. Wu, Coord. Chem. Rev. 2021, 444, 214038.
- 11Y. Li, J. Luo, S. Zhao, Acc. Chem. Res. 2022, 55, 3460.
- 12X. Liu, Y.-C. Yang, M.-Y. Li, L. Chen, L.-M. Wu, Chem. Soc. Rev. 2023, 52, 8699.
- 13M. Mutailipu, K. R. Poeppelmeier, S. Pan, Chem. Rev. 2021, 121, 1130.
- 14M. Mutailipu, M. Zhang, Z. Yang, S. Pan, Acc. Chem. Res. 2019, 52, 791.
- 15M. Mutailipu, Z. Yang, S. Pan, Acc. Mater. Res. 2021, 2, 282.
- 16L. Kang, F. Liang, X. Jiang, Z. Lin, C. Chen, Acc. Chem. Res. 2020, 53, 209.
- 17Z. Lin, X. Jiang, L. Kang, P. Gong, S. Luo, M.-H. Lee, J. Phys. D: Appl. Phys. 2014, 47, 253001.
- 18M. Luo, J. Sichuan. Nor. Univ.:Nat Sci Ed. 2024, 47, 1.
- 19L. Kang, S. Luo, H. Huang, N. Ye, Z. Lin, J. Qin, C. Chen, J. Phys. Chem. C. 2013, 117, 25684.
- 20Y. Shen, S. Zhao, J. Luo, Coord. Chem. Rev. 2018, 366, 1.
- 21C. Wu, G. Yang, M. G. Humphrey, C. Zhang, Coord. Chem. Rev. 2018, 375, 459.
- 22C. Wu, X. Jiang, Z. Wang, H. Sha, Z. Lin, Z. Huang, X. Long, M. G. Humphrey, C. Zhang, Angew. Chem., Int. Ed. 2021, 60, 14806.
- 23M. Luo, C. Lin, D. Lin, N. Ye, Angew Chem Int Ed 2020, 59, 15978.
- 24X. Wen, C. Lin, M. Luo, H. Fan, K. Chen, N. Ye, Sci. China Mater. 2021, 64, 2008.
- 25J.-X. Wang, S.-F. Li, M.-M. Ren, M.-H. Lv, R.-L. Tang, J. Chen, H. Huang, B. Zhang, D. Yan, Inorg. Chem. 2024, 63, 4487.
- 26D. Lin, M. Luo, C. Lin, F. Xu, N. Ye, J. Am. Chem. Soc. 2019, 141, 3390.
- 27L. Qi, X. Jiang, K. Duanmu, C. Wu, Z. Lin, Z. Huang, M. G. Humphrey, C. Zhang, J. Am. Chem. Soc. 2024, 146, 9975.
- 28J. Lu, Y.-K. Lian, L. Xiong, Q.-R. Wu, M. Zhao, K.-X. Shi, L. Chen, L.-M. Wu, J. Am. Chem. Soc. 2019, 141, 16151.
- 29H. Tian, C. Lin, Y. Zhou, X. Zhao, H. Fan, T. Yan, N. Ye, M. Luo, Angew Chem Int Ed 2023, 62, e202304858.
- 30L. Cao, H. Tian, D. Lin, C. Lin, F. Xu, Y. Han, T. Yan, J. Chen, B. Li, N. Ye, M. Luo, Chem. Sci. 2022, 13, 6990.
- 31L. Wu, C. Lin, H. Tian, Y. Zhou, H. Fan, S. Yang, N. Ye, M. Luo, Angew. Chem., Int. Ed. 2024, 63, e202315647.
- 32H. Tian, C. Lin, B. Li, X. Zhao, T. Yan, N. Ye, M. Luo, Adv. Funct. Mater. 2024, 34, 2402295.
- 33L. Xiong, L. Wu, L. Chen, Angew. Chem., Int. Ed. 2021, 60, 25063.
- 34G. M. Sheldrick, Acta Crystallogr A Found Crystallogr 2008, 64, 112.
- 35A. L. Spek, J. Appl. Crystallogr. 2003, 36, 7.
- 36R. Docherty, G. Clydesdale, K. J. Roberts, P. Bennema, J. Phys. D: Appl. Phys. 1991, 24, 89.
- 37H. Qiu, F. Li, C. Jin, Z. Yang, J. Li, S. Pan, M. Mutailipu, Angew. Chem., Int. Ed. 2024, 63, e202316194.
- 38C. Jin, F. Li, X. Li, J. Lu, Z. Yang, S. Pan, M. Mutailipu, Chem. Mater. 2022, 34, 7516.
- 39Z. Zhang, X. Liu, R. Wang, S. Zhao, W. He, H. Chen, X. Deng, L. Wu, Z. Zhou, L. Chen, Angew. Chem., Int. Ed. 2024, 63, e202408551.
- 40J. Lu, X. Liu, M. Zhao, X.-B. Deng, K.-X. Shi, Q.-R. Wu, L. Chen, M. Wu, J. Am. Chem. Soc. 2021, 143, 3647.
- 41Y. Kang, C. Yang, J. Gou, Y. Zhu, Q. Zhu, W. Xu, Q. Wu, Angew. Chem., Int. Ed. 2024, 63, e202402086.
- 42Q. Xia, X. Jiang, L. Qi, C. Wu, Z. Lin, Z. Huang, M. G. Humphrey, K. Tatsumi, C. Zhang, Inorg. Chem. Front. 2024, 11, 8813.
- 43C. Hu, C. Shen, H. Zhou, J. Han, Z. Yang, K. R. Poeppelmeier, F. Zhang, S. Pan, Small Struct. 2024, 5, 2400296.
- 44M. Zhang, B. Zhang, D. Yang, Y. Wang, Inorg. Chem. 2021, 60, 18483.
- 45Z. Bai, J. Lee, C.-L. Hu, G. Zou, K. M. Ok, Chem. Sci. 2024, 15, 6572.
- 46J. Yin, J. Guo, H. Huo, X. Liu, X. Cheng, Z. Lin, L. Wu, L. Chen, Angew. Chem., Int. Ed. 2024, 137, e202417579.
- 47M. Mutailipu, J. Han, Z. Li, F. Li, J. Li, F. Zhang, X. Long, Z. Yang, S. Pan, Nat. Photonics 2023, 17, 694.
- 48D. Eimerl, S. Velsko, L. Davis, F. Wang, G. Loiacono, G. Kennedy, IEEE J. Quantum Electron. 1989, 25, 179.
- 49S. K. Kurtz, T. T. Perry, J. Appl. Phys. 1968, 39, 3798.
- 50G. Kresse, J. Furthmüller, Comput. Mater. Sci. 1996, 6, 15.
- 51C. S. Wang, B. M. Klein, Phys. Rev. B 1981, 24, 3417.
- 52G. Kresse, J. Hafner, Phys. Rev. B 1993, 47, 558.
- 53C. Chen, A. Jiang, G. You, S. Lin, J. Opt. Soc. Am. B 1989, 6, 616 .
- 54Y. Mori, I. Kuroda, S. Nakajima, T. Sasaki, S. Nakai, Appl. Phys. Lett. 1995, 67, 1818.
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