The external electric field is a special strategy for generating novel structures.In this work,the intermolecular bonding and nonlinear optical properties are affected by applying an applied electric field of 0 to 9.7...The external electric field is a special strategy for generating novel structures.In this work,the intermolecular bonding and nonlinear optical properties are affected by applying an applied electric field of 0 to 9.77 V·nm^(-1)along the bonding direction of dimer of olympicenyl radical(OLY2).The results showed that the distance between molecular layers was lengthened gradually,and the 2e/20c bonds were weakened or even completely broken(the critical electric field is 9.77 V·nm^(-1))with the increase of the external electric field strength.Moreover,the introduction of an external electric field caused significant changes in the electronic properties of the OLY2,which induced charge transfer between inter-layer monomers,and enhanced the interlayer electrostatic interactions.Therefore,the external electric field not only regulates the interlayer interactions of molecules,but also causes the symmetric molecules to produce strong polarity,producing a large NLO response in OLY2.展开更多
A new candidate [Cu（PPh3）2Him]Br （1, PPh3 =triphenylphosphine, Him= 1-H-imidazole） for nonlinear optical （NLO） materials has been synthesized and characterized crystallographically. The third-order NLO optical p...A new candidate [Cu（PPh3）2Him]Br （1, PPh3 =triphenylphosphine, Him= 1-H-imidazole） for nonlinear optical （NLO） materials has been synthesized and characterized crystallographically. The third-order NLO optical properties were measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm. Compound 1 exhibits strong NLO absorptive abilities [a2=（61±5）×10^-12] and effective self-focusing performance [n2=（15±3）×10^-18 m^2·W^-1] in 1.01×10^-4 molodm 3 DMF solution. The compound also exhibits luminescence in DMF solution at room temperature and shows narrow emission with maximum at 382 nm. The electronic structure and photoluminescent process were investigated by means of TD-DFT calculations. The results suggest that the contribution to the frontier orbitals from the Cu-Br σ bond plays a crucial role in its linear optical properties, and the origin of luminescence is attrib- utable to the π＊ → n transitions.展开更多
In recent years, motivated by the discovery of deep-UV（wavelengths below 200 nm） nonlinear optical（NLO） phosphates, Ba3P3O（10）X（Cl, Br）, phosphates have entered into a passionate research era. In this review, ...In recent years, motivated by the discovery of deep-UV（wavelengths below 200 nm） nonlinear optical（NLO） phosphates, Ba3P3O（10）X（Cl, Br）, phosphates have entered into a passionate research era. In this review, recently discovered phosphate materials containing different anionic groups, i.e., isolated [PO4], [P2O7] dimer, [P3O（10）] trimer, and [PO3]∞ chain, are summarized, including their syntheses, structures, NLO performances and properties. Especially phosphates with short absorption edges in the deep-UV region and good SHG efficiency are introduced in detail. We hope that this work will present a clear view of the crystal chemistry of phosphates and promote the discovery of new high-performing second-order NLO materials to meet the urgent needs in laser science.展开更多
A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiola...A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh = thiophenolate) (1-4) were characterized by, elemental analysis, ER, UV NMR spectra and so on. The advantages of this method am summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high,purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although druid is an analogue to dmit.展开更多
The polarizabilities and hyperpolarizabilities of the tetrahydropyrrole diradical in different electronic states have been investigated using ab initio and density functional theory （DFT） methods combined with the f...The polarizabilities and hyperpolarizabilities of the tetrahydropyrrole diradical in different electronic states have been investigated using ab initio and density functional theory （DFT） methods combined with the finite field （FF） approach. The polarizability average value as is a maximum for the singlet state, while that for the closed-shell is a minimum. The trend in second hyperpolarizability average value yis in good agreement with that for as The yvalues of the singlet and triplet states are, respectively, about 3 and 2 times larger than that of the closed-shell. The order of the first hyperpolarizability total effective value βtot is βot （closed shell） βtot （singlet） 〉 βtot （triplet）. The as, βtot, and 7 values of different electronic states obtained using the B3LYP and MP4SDQ methods are close to those obtained using the reliable CCSD method. The nonlinear optical （NLO） properties of two systems isoelectronic with the tetrahydropyrrole diradical-cyclopentane and tetrahydrofuran diradicalsshow that the polarizabilities and hyperpolarizabilities of these systems are all smaller than those of the tetrahydropyrrole diradical in the three electronic states.展开更多
The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order...The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.展开更多
The p nitrophenylazo calixarene derivatives 1a-1d with nonlinear optical (NLO) properties were prepared by the diazo coupling reaction of calixarene with p nitrophenyl diazonium. The diazotization reaction ...The p nitrophenylazo calixarene derivatives 1a-1d with nonlinear optical (NLO) properties were prepared by the diazo coupling reaction of calixarene with p nitrophenyl diazonium. The diazotization reaction of p nitroaniline was carried out with isoamyl nitrite as a source of nitrous acid in EtONa/EtOH under refluxing condition. X Ray crystallographic analysis and 1H NMR spectra reveal that they exist as cone conformation in crystal state or in solution. HRS measurements at 1064 nm in THF indicate that p nitrophenylazo calixarenes have higher hyperpolarizability β z values than the corresponding reference compound 4 (4 nitrophenylazo) 2,6 dimethyl phenol, without red shift of the charge transfer band. The tetrakis p nitrophenylazo calixarene (2) with longer alkyl chains can form monolayer at the air/water interface.展开更多
Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) cha...Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) charge transfer characteristics of calculated molecules were studied and compared with corresponding experimental results. All the theoretical results agree well with the measurement. For 2 D molecule with two fold symmetry, the dominant charge transfer is off diagonal, while for three fold symmetry 2 D molecule, the dominant charge transfer is not only between branches and central group but also among branches.展开更多
The current study has obtained excellent potential nonlinear optical(NLO)materials by combining density functional theory methods with sum-over-states model to predict the second order NLO properties of helical graphe...The current study has obtained excellent potential nonlinear optical(NLO)materials by combining density functional theory methods with sum-over-states model to predict the second order NLO properties of helical graphene nanoribbons(HGNs)through introducing azulene defects or/and BN units.The introduction of these functional groups deforms the pristine HGN(compression or tension)and enhances obviously the static first hyperpolarizability(〈β0〉)of system by up to two orders of magnitude.The tensor components along the helical axis of HGNs play a dominant role in the total〈β0〉.The azulene defects and the BN units polarize the pristine HGN to different degrees,and the azulenes and contiguous benzenes are involved in the major electron excitations with significant contributions to〈β0〉but the BN units are not.The BN-doped chiral HGNs have good kinetic stability and strong second order NLO properties(6.84×10^(5)×10^(−30) esu),and can be a potential candidate of high-performance second order NLO materials.The predicted two-dimensional second order NLO spectra provide useful information for further exploration of those helicenes for electro-optic applications.展开更多
Phosphates are important candidates for ultraviolet/deep-ultraviolet(UV/DUV)nonlinear optical(NLO)materials by good transparency ability and variability of anion species as well as different coordinated cations.Phosph...Phosphates are important candidates for ultraviolet/deep-ultraviolet(UV/DUV)nonlinear optical(NLO)materials by good transparency ability and variability of anion species as well as different coordinated cations.Phosphates have been reported as minerals or NLO materials with abundant condensed anionic framework.For phosphate-based NLO materials,how to improve the second harmonic generation(SHG)response and birefringence re-mains a great challenge.Herein,this review analyzes the structure-property relationship of the representative UV/DUV phosphates,and the microscopic mechanism to achieve a balance between the short absorption edge and large SHG response is summarized.It provides a new idea to study the UV/DUV phosphate NLO materials.展开更多
Polymeric membranes with diverse structures have attracted much attention as new materials for nonlinear optical devices. In this report, a novel oligomer of poly(aromatic ether sulfone)(OAES) has been synthesized and...Polymeric membranes with diverse structures have attracted much attention as new materials for nonlinear optical devices. In this report, a novel oligomer of poly(aromatic ether sulfone)(OAES) has been synthesized and characterized. The electronic structure as well as linear and nonlinear optical properties has been studied by density function theory. The effect for general nonlinear optical polarizability of various condition has been further researched such as absence of side chains and introduction of phenyl substituent on side chains. The static and frequency-dependent hyperpolarizabilities of OAES and its derivatives have been calculated. This work interprets an efficient adjustment for the frequency response and the intensity of nonlinear optical polarizability can be achieved by regulating the structure of system, which provides a new potential for the application of oligomeric materials on nonlinear optical field.展开更多
Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of diffe...Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of different cyclometallated ligands(C∧N)and ancillary ligands[pyridme-2-carboxylate(pic)].It was found that the mo-dification of the LUMO energy levels was achieved by changing pic ligands and the energy gaps between the HOMO and LUMO were notably increased or decreased.In addition,the degree of conjugation was significantly changed with the substituent groups varied,which led to that the first hyperpolarizabilityβcould be effectively modulated.Through the analysis of time-dependent DFT(TD-DFT)results,we predicted that these studied complexes withπ→π^*charge transfer was beneficial to the large second-order NLO properties.Therefore,we hope that these studied iridium(III)complexes can be considered as versatile second-order NLO materials.展开更多
基金Foundation of Science and Technology Department of Jilin Province(20230101043JC).
文摘The external electric field is a special strategy for generating novel structures.In this work,the intermolecular bonding and nonlinear optical properties are affected by applying an applied electric field of 0 to 9.77 V·nm^(-1)along the bonding direction of dimer of olympicenyl radical(OLY2).The results showed that the distance between molecular layers was lengthened gradually,and the 2e/20c bonds were weakened or even completely broken(the critical electric field is 9.77 V·nm^(-1))with the increase of the external electric field strength.Moreover,the introduction of an external electric field caused significant changes in the electronic properties of the OLY2,which induced charge transfer between inter-layer monomers,and enhanced the interlayer electrostatic interactions.Therefore,the external electric field not only regulates the interlayer interactions of molecules,but also causes the symmetric molecules to produce strong polarity,producing a large NLO response in OLY2.
基金Acknowledgement This work was supported by the NSF of China （No. 20871072）, the NSF of Shandong Province （No. 2009ZRA02071）, the Scientific Development Plan of University in Shandong Province （No. J09LB53）, and the Doctoral Science Foundation of QUST.
文摘A new candidate [Cu（PPh3）2Him]Br （1, PPh3 =triphenylphosphine, Him= 1-H-imidazole） for nonlinear optical （NLO） materials has been synthesized and characterized crystallographically. The third-order NLO optical properties were measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm. Compound 1 exhibits strong NLO absorptive abilities [a2=（61±5）×10^-12] and effective self-focusing performance [n2=（15±3）×10^-18 m^2·W^-1] in 1.01×10^-4 molodm 3 DMF solution. The compound also exhibits luminescence in DMF solution at room temperature and shows narrow emission with maximum at 382 nm. The electronic structure and photoluminescent process were investigated by means of TD-DFT calculations. The results suggest that the contribution to the frontier orbitals from the Cu-Br σ bond plays a crucial role in its linear optical properties, and the origin of luminescence is attrib- utable to the π＊ → n transitions.
基金supported by the National Natural Science Foundation of China under Projects 91422303,21571020,and 21671023
文摘In recent years, motivated by the discovery of deep-UV（wavelengths below 200 nm） nonlinear optical（NLO） phosphates, Ba3P3O（10）X（Cl, Br）, phosphates have entered into a passionate research era. In this review, recently discovered phosphate materials containing different anionic groups, i.e., isolated [PO4], [P2O7] dimer, [P3O（10）] trimer, and [PO3]∞ chain, are summarized, including their syntheses, structures, NLO performances and properties. Especially phosphates with short absorption edges in the deep-UV region and good SHG efficiency are introduced in detail. We hope that this work will present a clear view of the crystal chemistry of phosphates and promote the discovery of new high-performing second-order NLO materials to meet the urgent needs in laser science.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 0 710 2 4) theEducationCommitteeofJiangsuProvince (No .0 0KJB15 0 0 0 1) .
文摘A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh = thiophenolate) (1-4) were characterized by, elemental analysis, ER, UV NMR spectra and so on. The advantages of this method am summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high,purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although druid is an analogue to dmit.
基金supported by the National Natural Science Foundation of China (20873017)the Program for Changjiang Scholars and Innovative Research Teams in University (IRT0714)
文摘The polarizabilities and hyperpolarizabilities of the tetrahydropyrrole diradical in different electronic states have been investigated using ab initio and density functional theory （DFT） methods combined with the finite field （FF） approach. The polarizability average value as is a maximum for the singlet state, while that for the closed-shell is a minimum. The trend in second hyperpolarizability average value yis in good agreement with that for as The yvalues of the singlet and triplet states are, respectively, about 3 and 2 times larger than that of the closed-shell. The order of the first hyperpolarizability total effective value βtot is βot （closed shell） βtot （singlet） 〉 βtot （triplet）. The as, βtot, and 7 values of different electronic states obtained using the B3LYP and MP4SDQ methods are close to those obtained using the reliable CCSD method. The nonlinear optical （NLO） properties of two systems isoelectronic with the tetrahydropyrrole diradical-cyclopentane and tetrahydrofuran diradicalsshow that the polarizabilities and hyperpolarizabilities of these systems are all smaller than those of the tetrahydropyrrole diradical in the three electronic states.
基金supported by the National Natural Science Foundation of China (20873017)the Natural Science Foundation of Jilin Province (20101154)
文摘The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .90 10 10 18)andtheCenterofMaterialsAnalysisofNanjingUniver sity .
文摘The p nitrophenylazo calixarene derivatives 1a-1d with nonlinear optical (NLO) properties were prepared by the diazo coupling reaction of calixarene with p nitrophenyl diazonium. The diazotization reaction of p nitroaniline was carried out with isoamyl nitrite as a source of nitrous acid in EtONa/EtOH under refluxing condition. X Ray crystallographic analysis and 1H NMR spectra reveal that they exist as cone conformation in crystal state or in solution. HRS measurements at 1064 nm in THF indicate that p nitrophenylazo calixarenes have higher hyperpolarizability β z values than the corresponding reference compound 4 (4 nitrophenylazo) 2,6 dimethyl phenol, without red shift of the charge transfer band. The tetrakis p nitrophenylazo calixarene (2) with longer alkyl chains can form monolayer at the air/water interface.
文摘Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) charge transfer characteristics of calculated molecules were studied and compared with corresponding experimental results. All the theoretical results agree well with the measurement. For 2 D molecule with two fold symmetry, the dominant charge transfer is off diagonal, while for three fold symmetry 2 D molecule, the dominant charge transfer is not only between branches and central group but also among branches.
基金supported by the National Natural Science Foundation of China(No.21673025)the Open Projects of the Key Laboratory of Polyoxometalate Science of Ministry of Education(NENU),China and the Project of the State Key Laboratory of Supramolecular Structure and Materials(JLU),China(No.SKLSSM2021020).
文摘The current study has obtained excellent potential nonlinear optical(NLO)materials by combining density functional theory methods with sum-over-states model to predict the second order NLO properties of helical graphene nanoribbons(HGNs)through introducing azulene defects or/and BN units.The introduction of these functional groups deforms the pristine HGN(compression or tension)and enhances obviously the static first hyperpolarizability(〈β0〉)of system by up to two orders of magnitude.The tensor components along the helical axis of HGNs play a dominant role in the total〈β0〉.The azulene defects and the BN units polarize the pristine HGN to different degrees,and the azulenes and contiguous benzenes are involved in the major electron excitations with significant contributions to〈β0〉but the BN units are not.The BN-doped chiral HGNs have good kinetic stability and strong second order NLO properties(6.84×10^(5)×10^(−30) esu),and can be a potential candidate of high-performance second order NLO materials.The predicted two-dimensional second order NLO spectra provide useful information for further exploration of those helicenes for electro-optic applications.
基金supprted by the National Natural Science Foundation of China(51962033)the Xinjiang Major Science and Technology Project(2021A01001-3).
文摘Phosphates are important candidates for ultraviolet/deep-ultraviolet(UV/DUV)nonlinear optical(NLO)materials by good transparency ability and variability of anion species as well as different coordinated cations.Phosphates have been reported as minerals or NLO materials with abundant condensed anionic framework.For phosphate-based NLO materials,how to improve the second harmonic generation(SHG)response and birefringence re-mains a great challenge.Herein,this review analyzes the structure-property relationship of the representative UV/DUV phosphates,and the microscopic mechanism to achieve a balance between the short absorption edge and large SHG response is summarized.It provides a new idea to study the UV/DUV phosphate NLO materials.
基金financial support of the 100-Talent Program of Chinese Academy of Sciences。
文摘Polymeric membranes with diverse structures have attracted much attention as new materials for nonlinear optical devices. In this report, a novel oligomer of poly(aromatic ether sulfone)(OAES) has been synthesized and characterized. The electronic structure as well as linear and nonlinear optical properties has been studied by density function theory. The effect for general nonlinear optical polarizability of various condition has been further researched such as absence of side chains and introduction of phenyl substituent on side chains. The static and frequency-dependent hyperpolarizabilities of OAES and its derivatives have been calculated. This work interprets an efficient adjustment for the frequency response and the intensity of nonlinear optical polarizability can be achieved by regulating the structure of system, which provides a new potential for the application of oligomeric materials on nonlinear optical field.
基金the“12th Five-year”Science and Technology Research Project of the Education Departaent of Jilin Province,China(No.[2016]494)and the National Natural Science Foundation of China(No.21173035).
文摘Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of different cyclometallated ligands(C∧N)and ancillary ligands[pyridme-2-carboxylate(pic)].It was found that the mo-dification of the LUMO energy levels was achieved by changing pic ligands and the energy gaps between the HOMO and LUMO were notably increased or decreased.In addition,the degree of conjugation was significantly changed with the substituent groups varied,which led to that the first hyperpolarizabilityβcould be effectively modulated.Through the analysis of time-dependent DFT(TD-DFT)results,we predicted that these studied complexes withπ→π^*charge transfer was beneficial to the large second-order NLO properties.Therefore,we hope that these studied iridium(III)complexes can be considered as versatile second-order NLO materials.
