Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra
Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we...
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| Veröffentlicht in: | Journal of the American Chemical Society 2021-03, Vol.143 (11), p.4138-4142 |
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| container_title | Journal of the American Chemical Society |
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| creator | Wu, Chao Wu, Tianhui Jiang, Xingxing Wang, Zujian Sha, Hongyuan Lin, Lin Lin, Zheshuai Huang, Zhipeng Long, Xifa Humphrey, Mark G Zhang, Chi |
| description | Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials. |
| doi_str_mv | 10.1021/jacs.1c00416 |
| format | Article |
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However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.1c00416</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2021-03, Vol.143 (11), p.4138-4142</ispartof><rights>2021 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0002-9192-8431 ; 0000-0002-1554-8883 ; 0000-0002-5237-8916 ; 0000-0001-6068-8773 ; 0000-0002-4433-6783 ; 0000-0002-9829-9893 ; 0000-0002-8016-0359 ; 0000-0002-7113-2903 ; 0000-0003-2960-9461</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jacs.1c00416$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jacs.1c00416$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,27055,27903,27904,56717,56767</link.rule.ids></links><search><creatorcontrib>Wu, Chao</creatorcontrib><creatorcontrib>Wu, Tianhui</creatorcontrib><creatorcontrib>Jiang, Xingxing</creatorcontrib><creatorcontrib>Wang, Zujian</creatorcontrib><creatorcontrib>Sha, Hongyuan</creatorcontrib><creatorcontrib>Lin, Lin</creatorcontrib><creatorcontrib>Lin, Zheshuai</creatorcontrib><creatorcontrib>Huang, Zhipeng</creatorcontrib><creatorcontrib>Long, Xifa</creatorcontrib><creatorcontrib>Humphrey, Mark G</creatorcontrib><creatorcontrib>Zhang, Chi</creatorcontrib><title>Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. 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Am. Chem. Soc</addtitle><date>2021-03-24</date><risdate>2021</risdate><volume>143</volume><issue>11</issue><spage>4138</spage><epage>4142</epage><pages>4138-4142</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. 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| title | Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra |
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