The title compound, C16H20INo3, crystallizes in space group P1 (#2),triclinic, a=7. 970(1), b=9. 098(1), c= 12. 910(2) A, a=90. 00(1), β=81. 63(1), γ=65. 75(1)°, V=842. 6(2) A 3, Z=2, Dc= 1. 581 g/cm3,μ(MoKa) ...The title compound, C16H20INo3, crystallizes in space group P1 (#2),triclinic, a=7. 970(1), b=9. 098(1), c= 12. 910(2) A, a=90. 00(1), β=81. 63(1), γ=65. 75(1)°, V=842. 6(2) A 3, Z=2, Dc= 1. 581 g/cm3,μ(MoKa) = 1. 909mm-1, F(000) =400. The final R and (F2)R are 0. 0269 and0. 0632 for 2903 observed reflections (I>2σ(I) ), respectively. In the title molecule, two configurations,A and B were found for the slightly twisted cations, which take the same occupancy inthe crystal equally. Cations are connected through anions 1- and crystallized water,and anti-parallelly packed through intermolecular weak hydrogen bonding, van derWaals interactions and strong π-π interaction.展开更多
[Zn(POM)_2Br_2](POM is 3-Methyl-4-Nitropyridine-1-Oxide),C_(12)H_(12)Br_2N_4O_6Zn, Mr=533.44,triclinic,P1,a=11.450(3),b=13.027(2),c=6.605(1),α=101.25(1),β=96.96(2), γ=108.06(2)°,V=901.2(4)~3,Z=2,D_c=1.97g·...[Zn(POM)_2Br_2](POM is 3-Methyl-4-Nitropyridine-1-Oxide),C_(12)H_(12)Br_2N_4O_6Zn, Mr=533.44,triclinic,P1,a=11.450(3),b=13.027(2),c=6.605(1),α=101.25(1),β=96.96(2), γ=108.06(2)°,V=901.2(4)~3,Z=2,D_c=1.97g·cm^(-3),(MoK_α)=0.71069,F(000)=520, μ=58.21cm^(-1),final R=0.040 for 2192 observed reflections,T=296K.The compound is a mononuclear complex,containing a tetrahedrally coordinated zinc atom.展开更多
The SHG effects of substituted 3-thienyl chalcone compounds weremeasured. The relationship between structure and effect of substituted 3-thienyl chal-cone derivatives and substituted 2-thienyl chalcone derivatives wer...The SHG effects of substituted 3-thienyl chalcone compounds weremeasured. The relationship between structure and effect of substituted 3-thienyl chal-cone derivatives and substituted 2-thienyl chalcone derivatives were discussed. It isshown that their properties of high SHG efficient are similar to each other and the sub-stituted 3-thienyl chalcone molecules are easier to form non-centrosymmetric crystalstructure than substituted 2-thienyl chalcone molecules.展开更多
The crystal of 2, 4, 6-tristyryl-s-triazine (TSTA) has been prepared and its crystal structure been determined to be in the polar non-centrosymmetric space group Cmc21. The molecular structure of TSTA is characterize...The crystal of 2, 4, 6-tristyryl-s-triazine (TSTA) has been prepared and its crystal structure been determined to be in the polar non-centrosymmetric space group Cmc21. The molecular structure of TSTA is characterized by the slightly curved planar configuration and the octupolar C3v molecular symmetry. As expected, TSTA crystal shows a quite novel nonlinear optical (NLO) property with its powder second harmonic generating (SHG) intensity of 1.8 times as that of urea. It also shows excellent transparency (with the peak position of 322 nm in absorption spectrum) and good thermal stability (with the melting point of 225-229C).展开更多
Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects.Here a n...Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects.Here a novel ionic compound 2(BPP)^(+)·[Mn(NCS)_(4)]^(2-)(1)was synthesized via the assembly of benzyltriphenylphosphorus chloride,isothiocyanate and manganese chloride,which displays both strong SHG response and purple luminescence.Compound 1 belongs to monoclinic system and crystallizes in Cc space group.X-ray single-crystal diffraction analysis shows that Mn^(2+)ions are tetra-coordinated with N atoms of four NCS-ions through forming a distorted tetrahedral configuration.The anion Mn(NCS)42-forms a 1D chain structure through strong S…S interaction.At the same time,there are abundant C–H…S andπ···πinteractions,which further accumulate into a three-dimensional supramolecular structure.Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm.In particular,the second harmonic generation(SHG)measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate(KDP).This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.展开更多
BiB3O6 (BIBO) single crystals with size of 46×23×10 mm3 and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed ...BiB3O6 (BIBO) single crystals with size of 46×23×10 mm3 and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB3O6 is C2 and the cell parameters are a=7.1203(7) ?, b=4.9948(7) ?, c=6.5077(7) ?, β=105.586(8)″, and V=222.93(5) ?3. The density of BIBO is 4.8965 g/cm3. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB3O6 is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB3O6 is a kind of excellent nonlinear optical (NLO) crystal.展开更多
Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. Th...Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. They exhibit wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as moderately high thermal stability. In this paper, the structures and properties of the metal iodates are reviewed. The combination of d0 transition-metal cations with the iodate groups afforded a large number of metal iodates, with cations covering alkali metal, alkaline earth and lanthanide elements. Many of them are noncentrosymmetric (NCS) and display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Some lanthanide iodates are able to emit strong luminescence in the visible or near-IR regions. The use of transition metal ions with dn (n ≠ 0) electronic configuration into iodate systems can also induce the formation of NCS compounds when the lone pairs of the iodate groups are properly aligned. The dn transition metal cations are normally octahedrally coordinated or in a square-planar coordination geometry. Furthermore, the combination of two different types of lone-pair-containing cations is also an effective strategy to design new SHG materials.展开更多
Three s-triazine derivatives have been synthesized and their structures been de-termined. These are Compound I: 2,4-dimethyl-6-(p-N,N-dimethylaminostyryl)-s-triazine (abbre-viated to NMe-1), Compound II: 2,4-dimethyl-...Three s-triazine derivatives have been synthesized and their structures been de-termined. These are Compound I: 2,4-dimethyl-6-(p-N,N-dimethylaminostyryl)-s-triazine (abbre-viated to NMe-1), Compound II: 2,4-dimethyl-6-(p-N,N-diethylaminostyryl)-s-triazine (to NEt-1), and Compound III: 2-methyl-4,6-bis(p-N,N-dimethylaminostyryl)-s-triazine (NMe-2). NMe-1 and NEt-1 molecules belong to the D-π-A type with a one-dimensional charge-transfer character. NMe-1 crystallizes to centrosymmetric P1 space group, while NEt-1 to non-centrosymmetric polar Cc space group with all of the molecular charge-transfer axes taking the same orientation. Under the irradiation of 1064 nm fundamental laser, NEt-1 powder crystals radiate a 2-order harmonic light with an intensity 46.8 times that of urea. The Λ typed NMe-2 molecule, which has a two-dimensional charge-transfer character, crystallizes to polar P21 space group. Its powder crystals exhibit a 2-order harmonic intensity 46.2 times that of urea. The quantum chemical cal-culations and tensor analyses have been carried out to reveal the dependence of the macro 2-order nonlinear optical (NLO) efficiency on the micro 2-order NLO coefficients (β) and on the crystalline packing styles.展开更多
Two phase transition materials[iPrQ]2MnBr4(1,iPrQ=N-isopropyl-quinuclidinium)and[iPrQ]_(2)MnCl_(4)(2)were synthesized and characterized.Dielectric measurements and differential scanning calorimetry showed that the two...Two phase transition materials[iPrQ]2MnBr4(1,iPrQ=N-isopropyl-quinuclidinium)and[iPrQ]_(2)MnCl_(4)(2)were synthesized and characterized.Dielectric measurements and differential scanning calorimetry showed that the two compounds underwent reversible phase transitions at ca.–47 and–37℃,respectively.Variable-temperature single-crystal X-ray diffraction suggested that the two compounds underwent the same phase transitions from space group C2/c to Cc but at different temperature.The variable crystal structures indicated that the structural phase transitions of the compound were ascribed to the torsional movement of quinuclidine ring and the disappearance of the c-slide plane.The second harmonic generation(SHG)response further proved this structural phase transition.Fluorescence tests showed that the two compounds have strong fluorescence.The strong variations in dielectric anomalies make compounds 1 and 2 suitable for promising switchable dielectric materials.展开更多
文摘The title compound, C16H20INo3, crystallizes in space group P1 (#2),triclinic, a=7. 970(1), b=9. 098(1), c= 12. 910(2) A, a=90. 00(1), β=81. 63(1), γ=65. 75(1)°, V=842. 6(2) A 3, Z=2, Dc= 1. 581 g/cm3,μ(MoKa) = 1. 909mm-1, F(000) =400. The final R and (F2)R are 0. 0269 and0. 0632 for 2903 observed reflections (I>2σ(I) ), respectively. In the title molecule, two configurations,A and B were found for the slightly twisted cations, which take the same occupancy inthe crystal equally. Cations are connected through anions 1- and crystallized water,and anti-parallelly packed through intermolecular weak hydrogen bonding, van derWaals interactions and strong π-π interaction.
文摘[Zn(POM)_2Br_2](POM is 3-Methyl-4-Nitropyridine-1-Oxide),C_(12)H_(12)Br_2N_4O_6Zn, Mr=533.44,triclinic,P1,a=11.450(3),b=13.027(2),c=6.605(1),α=101.25(1),β=96.96(2), γ=108.06(2)°,V=901.2(4)~3,Z=2,D_c=1.97g·cm^(-3),(MoK_α)=0.71069,F(000)=520, μ=58.21cm^(-1),final R=0.040 for 2192 observed reflections,T=296K.The compound is a mononuclear complex,containing a tetrahedrally coordinated zinc atom.
文摘The SHG effects of substituted 3-thienyl chalcone compounds weremeasured. The relationship between structure and effect of substituted 3-thienyl chal-cone derivatives and substituted 2-thienyl chalcone derivatives were discussed. It isshown that their properties of high SHG efficient are similar to each other and the sub-stituted 3-thienyl chalcone molecules are easier to form non-centrosymmetric crystalstructure than substituted 2-thienyl chalcone molecules.
基金This work was supported by the National Natural Science Foundation of China(No.20172034)Foundation for University Key Teacber by Ministry of Education,and the grant for state key program of China.
文摘The crystal of 2, 4, 6-tristyryl-s-triazine (TSTA) has been prepared and its crystal structure been determined to be in the polar non-centrosymmetric space group Cmc21. The molecular structure of TSTA is characterized by the slightly curved planar configuration and the octupolar C3v molecular symmetry. As expected, TSTA crystal shows a quite novel nonlinear optical (NLO) property with its powder second harmonic generating (SHG) intensity of 1.8 times as that of urea. It also shows excellent transparency (with the peak position of 322 nm in absorption spectrum) and good thermal stability (with the melting point of 225-229C).
基金the National Natural Science Foundation of China(NOS.21761013,21671086 and 21471070)。
文摘Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects.Here a novel ionic compound 2(BPP)^(+)·[Mn(NCS)_(4)]^(2-)(1)was synthesized via the assembly of benzyltriphenylphosphorus chloride,isothiocyanate and manganese chloride,which displays both strong SHG response and purple luminescence.Compound 1 belongs to monoclinic system and crystallizes in Cc space group.X-ray single-crystal diffraction analysis shows that Mn^(2+)ions are tetra-coordinated with N atoms of four NCS-ions through forming a distorted tetrahedral configuration.The anion Mn(NCS)42-forms a 1D chain structure through strong S…S interaction.At the same time,there are abundant C–H…S andπ···πinteractions,which further accumulate into a three-dimensional supramolecular structure.Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm.In particular,the second harmonic generation(SHG)measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate(KDP).This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.
基金This work was supported by a Grant for the State Key Program of China.
文摘BiB3O6 (BIBO) single crystals with size of 46×23×10 mm3 and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB3O6 is C2 and the cell parameters are a=7.1203(7) ?, b=4.9948(7) ?, c=6.5077(7) ?, β=105.586(8)″, and V=222.93(5) ?3. The density of BIBO is 4.8965 g/cm3. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB3O6 is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB3O6 is a kind of excellent nonlinear optical (NLO) crystal.
基金supported by the National Natural Science Foundation of China (20731006, 20825104 & 21003127)
文摘Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. They exhibit wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as moderately high thermal stability. In this paper, the structures and properties of the metal iodates are reviewed. The combination of d0 transition-metal cations with the iodate groups afforded a large number of metal iodates, with cations covering alkali metal, alkaline earth and lanthanide elements. Many of them are noncentrosymmetric (NCS) and display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Some lanthanide iodates are able to emit strong luminescence in the visible or near-IR regions. The use of transition metal ions with dn (n ≠ 0) electronic configuration into iodate systems can also induce the formation of NCS compounds when the lone pairs of the iodate groups are properly aligned. The dn transition metal cations are normally octahedrally coordinated or in a square-planar coordination geometry. Furthermore, the combination of two different types of lone-pair-containing cations is also an effective strategy to design new SHG materials.
基金the National Natural Science Foundation of China(Grant Nos.20472044&20172034) the PhD.Programs Foundation of the Ministry of Education of China.
文摘Three s-triazine derivatives have been synthesized and their structures been de-termined. These are Compound I: 2,4-dimethyl-6-(p-N,N-dimethylaminostyryl)-s-triazine (abbre-viated to NMe-1), Compound II: 2,4-dimethyl-6-(p-N,N-diethylaminostyryl)-s-triazine (to NEt-1), and Compound III: 2-methyl-4,6-bis(p-N,N-dimethylaminostyryl)-s-triazine (NMe-2). NMe-1 and NEt-1 molecules belong to the D-π-A type with a one-dimensional charge-transfer character. NMe-1 crystallizes to centrosymmetric P1 space group, while NEt-1 to non-centrosymmetric polar Cc space group with all of the molecular charge-transfer axes taking the same orientation. Under the irradiation of 1064 nm fundamental laser, NEt-1 powder crystals radiate a 2-order harmonic light with an intensity 46.8 times that of urea. The Λ typed NMe-2 molecule, which has a two-dimensional charge-transfer character, crystallizes to polar P21 space group. Its powder crystals exhibit a 2-order harmonic intensity 46.2 times that of urea. The quantum chemical cal-culations and tensor analyses have been carried out to reveal the dependence of the macro 2-order nonlinear optical (NLO) efficiency on the micro 2-order NLO coefficients (β) and on the crystalline packing styles.
基金supported by the National Natural Science Foundation of China(21671084)the Six talent peaks project in Jiangsu Province(2014-XCL-008)the Qing Lan Project of Jiangsu Province and the Foundation of Jiangsu Educational Committee(16KJB430011)。
文摘Two phase transition materials[iPrQ]2MnBr4(1,iPrQ=N-isopropyl-quinuclidinium)and[iPrQ]_(2)MnCl_(4)(2)were synthesized and characterized.Dielectric measurements and differential scanning calorimetry showed that the two compounds underwent reversible phase transitions at ca.–47 and–37℃,respectively.Variable-temperature single-crystal X-ray diffraction suggested that the two compounds underwent the same phase transitions from space group C2/c to Cc but at different temperature.The variable crystal structures indicated that the structural phase transitions of the compound were ascribed to the torsional movement of quinuclidine ring and the disappearance of the c-slide plane.The second harmonic generation(SHG)response further proved this structural phase transition.Fluorescence tests showed that the two compounds have strong fluorescence.The strong variations in dielectric anomalies make compounds 1 and 2 suitable for promising switchable dielectric materials.
