High-performance bi-functional materials are in urgent demand for the next-generation integrated optical devices.In this work,we successfully synthesized the first tricyanomelaminate with bi-functional optical respons...High-performance bi-functional materials are in urgent demand for the next-generation integrated optical devices.In this work,we successfully synthesized the first tricyanomelaminate with bi-functional optical responses,namely Cs_(3)C_(6)N_(9)•H_(2)O(I),from its analogue Na_(3)C_(6)N_(9)•3H_(2)O by a facile ion exchange method.In contrast to Na_(3)C_(6)N_(9)•3H_(2)O,I realizes an optimal arrangement of𝜋π-conjugated(C_(6)N_(9))3−anion groups in its crystal structure.As a result,the second-order nonlinear optical(NLO)response is greatly enhanced from nearly zero of Na_(3)C_(6)N_(9)•3H_(2)O to∼9.8×KH_(2)PO_(4)of I.Furthermore,I exhibits a giant linear optical anisotropic response(i.e.birefringence)of 0.52 at the wavelength of 550 nm.Both responses are almost the largest among the inorganic compounds ofπ-conjugated rings,which indicates that I has great potential as a bi-functional optical crystal.Structural and theoretical analyses reveal the microscopic origin of excellent optical properties.This work would attract a lot of interest to the persistently neglected potential of tricyanomelaminates as linear optical and NLO crystals.展开更多
Conventional wisdom says that nonpolar structures do not favorably produce strong second-harmonic generation(SHG)responses since the polarization in their microscopic functional groups are counteracted.Herein,we repor...Conventional wisdom says that nonpolar structures do not favorably produce strong second-harmonic generation(SHG)responses since the polarization in their microscopic functional groups are counteracted.Herein,we report the first nonlinear optical thiosulfate,Na_(10)Cd(NO_(3))_(4)(SO_(3)S)_(4),which crystallizes in a nonpolar space group of P−4.However,this thiosulfate exhibits a strong SHG response of about 4.2 times that of the benchmark KH2PO4,which is larger than those of polar sulfates.According to first-principles calculations and a flexible dipole model,the SHG enhancement is mainly ascribed to the larger flexibility of the S=S bond in the SO_(3)S tetrahedra in comparison with the S–O bond in the SO4 tetrahedra.These findings indicate that constructing flexible bonds is an effective strategy to design highperformance nonlinear optical materials regardless of polarity.展开更多
Two fluoride sulfates,K_(2)Mn_(3)(SO_(4))_(3)F_(2)·4H_(2)O(Ⅰ) and Rb_(2)Mn_(3)(SO_(4))_(3)F_(2)·2H_(2)O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that th...Two fluoride sulfates,K_(2)Mn_(3)(SO_(4))_(3)F_(2)·4H_(2)O(Ⅰ) and Rb_(2)Mn_(3)(SO_(4))_(3)F_(2)·2H_(2)O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_(1.)Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn_(3)(SO_(4))3F_(2)(H_(2)O)2]_(∞) layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH_(2)PO_(4).展开更多
基金This work was financially supported by the National Natural Science Foundation of China(22122507,21833010,61975207,22193042,and 21921001)the Natural Science Foundation of Fujian Province(2022J02012)+2 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Y202069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LY-SLH024)as well as Fujian Institute of Innovation(FJCXY18010201)in the Chinese Academy of Sciences.
基金the National Natural Science Foundation of China(22122507,21833010,61975207 and 21921001)the Youth Innovation Promotion of Chinese Academy of Sciences(Y202069)+1 种基金the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LY-SLH024)Fujian Institute of Innovation(FJCXY18010201)in Chinese Academy of Sciences。
文摘High-performance bi-functional materials are in urgent demand for the next-generation integrated optical devices.In this work,we successfully synthesized the first tricyanomelaminate with bi-functional optical responses,namely Cs_(3)C_(6)N_(9)•H_(2)O(I),from its analogue Na_(3)C_(6)N_(9)•3H_(2)O by a facile ion exchange method.In contrast to Na_(3)C_(6)N_(9)•3H_(2)O,I realizes an optimal arrangement of𝜋π-conjugated(C_(6)N_(9))3−anion groups in its crystal structure.As a result,the second-order nonlinear optical(NLO)response is greatly enhanced from nearly zero of Na_(3)C_(6)N_(9)•3H_(2)O to∼9.8×KH_(2)PO_(4)of I.Furthermore,I exhibits a giant linear optical anisotropic response(i.e.birefringence)of 0.52 at the wavelength of 550 nm.Both responses are almost the largest among the inorganic compounds ofπ-conjugated rings,which indicates that I has great potential as a bi-functional optical crystal.Structural and theoretical analyses reveal the microscopic origin of excellent optical properties.This work would attract a lot of interest to the persistently neglected potential of tricyanomelaminates as linear optical and NLO crystals.
基金supported by the National Natural Science Foundation of China(nos.21833010,61975207,21921001,21971238,51872297,and 51890864)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(no.ZDBS-LY-SLH024)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(nos.XDB20010200 and XDB20000000)Fujian Institute of Innovation(no.FJCXY18010201)in Chinese Academy of Sciences,the National Key Research and Development Program of China(no.2019YFA0210400)Key Laboratory of Functional Crystals and Laser Tech-nology,TIPC,CAS(no.FCLT 202003)as well as Key Laboratory of New Processing Technology for Nonferrous Metal&Materials,Ministry of Education/Guangxi Key Laboratory of Optical and Electronic Materials and Devices(no.20KF-11).
文摘Conventional wisdom says that nonpolar structures do not favorably produce strong second-harmonic generation(SHG)responses since the polarization in their microscopic functional groups are counteracted.Herein,we report the first nonlinear optical thiosulfate,Na_(10)Cd(NO_(3))_(4)(SO_(3)S)_(4),which crystallizes in a nonpolar space group of P−4.However,this thiosulfate exhibits a strong SHG response of about 4.2 times that of the benchmark KH2PO4,which is larger than those of polar sulfates.According to first-principles calculations and a flexible dipole model,the SHG enhancement is mainly ascribed to the larger flexibility of the S=S bond in the SO_(3)S tetrahedra in comparison with the S–O bond in the SO4 tetrahedra.These findings indicate that constructing flexible bonds is an effective strategy to design highperformance nonlinear optical materials regardless of polarity.
基金financially supported by the National Natural Science Foundation of China(Nos.21833010,21525104,21971238,61975207,21921001)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBS-LYSLH024)+1 种基金Key Laboratory of Functional Crystals and Laser Technology,TIPC,CAS(No.FCLT 202003)Key Laboratory of New Processing Technology for Nonferrous Metal&Materials,Ministry of Education/Guangxi Key Laboratory of Optical and Electronic Materials and Devices(No.20KF-11)。
文摘Two fluoride sulfates,K_(2)Mn_(3)(SO_(4))_(3)F_(2)·4H_(2)O(Ⅰ) and Rb_(2)Mn_(3)(SO_(4))_(3)F_(2)·2H_(2)O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_(1.)Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn_(3)(SO_(4))3F_(2)(H_(2)O)2]_(∞) layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH_(2)PO_(4).
