多支链含给—受体结构的共轭铂（Ⅱ）芳香炔配合物的合成及其非线性光学性质研究
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摘要
铂芳香炔低聚物是近几年研究比较多的一类新型重金属芳香炔类低聚物,这类物质包含了铂乙炔结构单元和大的电子共轭系统,这为其提供了一些独特的光物理性能,特别是在非线性光学材料方面展现出优良的应用前景。过渡金属离子的d轨道和共轭π电子的自旋-耦合轨道作用使含有重金属离子和刚性结构的分子能够表现出大的反饱和吸收特性。
本论文选择了铂炔类化合物作为研究对象,合成了一系列含有给-受体结构的三支链铂芳香炔共轭低聚物(1-6)。利用元素分析、核磁共振氢谱、质谱等技术手段对它们的结构进行了表征。
对所有目标化合物的紫外-可见吸收光谱特性、荧光和荧光量子产率、反饱和吸收和一阶超极化率进行了初步研究。三嗪为中心的配合物(1-3)的最大吸收相对于三苯胺为中心的配合物(4-6)的最大吸收红移38-40nm。配合物4-6在空气饱和的氯仿溶液中的发射光谱显示两个主要发射峰。其中具有更短的波长的峰归因于它们的荧光,具有较长的波长的峰归因于他们的磷光。然而,化合物1～3在空气饱和的氯仿溶液中只检测到了荧光。用溶致变色法测定了6个目标化合物的分子的一阶超极化率在4.06×10-29～2.11×10-28cm5/esu范围,比一些常见的非线性光学的材料的一阶超极化率高出很多。利用开孔Z-扫描技术对目标化合物的非线性吸收特性进行了测试,结果表明化合物2和5表现出良好的非线性光学性能,化合物1～6的σeff/σo的值在2-22之间,σeff->σ0,说明了这类化合物具有比较好的反饱和吸收特征。
Platinum acetylides are a new type of heavy metal aromatic alkynes that have been researched intensively in recent years. The heavy metallic ion and the large π-conjugated systems confer these organometallic oligomers great unique properties, especially the great nonlinear optical property. Molecules containing heavy metal ions and rigid structures always exhibit large reverse saturable absorption due to the spin-orbit coupling between the d orbital of the transition metal ion and the conjugate π electron, which can enhance their reverse saturable absorption properties greatly.
In this thesis, a series of conjugated platinum (II) acetylide complexes with multi-branched donor-acceptor structures (1-6) were synthesized. The target products were characterized via elemental analysis,'HNMR, MS, etc., respectively.
The UV-vis absorption spectra, luminescence spectra, fluorescence quantum yields, and phosphorescence quantum yields of these complexes1-6were tested. Finally the nonlinear absorption and the first order hyperpolarizability were measured using open aperture Z-scan technique and solvatochromic method, respectively. The absorption maxima of the triazine-centered complexes (1-3) are38-40nm red-shifted compared to those of the triphenylamine-centered complexes (4～6). The luminescence spectra of the complexes4-6in air-saturated chloroform showed two main emission peaks, in which the peak with shorter wavelength was ascribed to their fluorescence, and the peak with longer wavelength was ascribed to their phosphorescence. However, only the fluorescence has been detected for1～3in air-saturated chloroform. The molecular first order hyperpolarizabilities of the six target compounds were tested using solvatochromic method, and their molecular hyperpolarizabilities are in the range of4.06×10-29～2.11×10-28cm5/esu, which is much higher than that of some other common nonlinear optical materials. The results indicated that complexes2and5exhibit excellent nonlinear absorption properties. The ratios of the effective nonlinear absorption cross section to ground-state absorption cross section σeff/σ0of complexes1～6are in the range of4～22, aeffis far bigger than σ0, which indicates that this kind of compounds has the characteristics of the saturated absorption.
本论文选择了铂炔类化合物作为研究对象,合成了一系列含有给-受体结构的三支链铂芳香炔共轭低聚物(1-6)。利用元素分析、核磁共振氢谱、质谱等技术手段对它们的结构进行了表征。
对所有目标化合物的紫外-可见吸收光谱特性、荧光和荧光量子产率、反饱和吸收和一阶超极化率进行了初步研究。三嗪为中心的配合物(1-3)的最大吸收相对于三苯胺为中心的配合物(4-6)的最大吸收红移38-40nm。配合物4-6在空气饱和的氯仿溶液中的发射光谱显示两个主要发射峰。其中具有更短的波长的峰归因于它们的荧光,具有较长的波长的峰归因于他们的磷光。然而,化合物1～3在空气饱和的氯仿溶液中只检测到了荧光。用溶致变色法测定了6个目标化合物的分子的一阶超极化率在4.06×10-29～2.11×10-28cm5/esu范围,比一些常见的非线性光学的材料的一阶超极化率高出很多。利用开孔Z-扫描技术对目标化合物的非线性吸收特性进行了测试,结果表明化合物2和5表现出良好的非线性光学性能,化合物1～6的σeff/σo的值在2-22之间,σeff->σ0,说明了这类化合物具有比较好的反饱和吸收特征。
Platinum acetylides are a new type of heavy metal aromatic alkynes that have been researched intensively in recent years. The heavy metallic ion and the large π-conjugated systems confer these organometallic oligomers great unique properties, especially the great nonlinear optical property. Molecules containing heavy metal ions and rigid structures always exhibit large reverse saturable absorption due to the spin-orbit coupling between the d orbital of the transition metal ion and the conjugate π electron, which can enhance their reverse saturable absorption properties greatly.
In this thesis, a series of conjugated platinum (II) acetylide complexes with multi-branched donor-acceptor structures (1-6) were synthesized. The target products were characterized via elemental analysis,'HNMR, MS, etc., respectively.
The UV-vis absorption spectra, luminescence spectra, fluorescence quantum yields, and phosphorescence quantum yields of these complexes1-6were tested. Finally the nonlinear absorption and the first order hyperpolarizability were measured using open aperture Z-scan technique and solvatochromic method, respectively. The absorption maxima of the triazine-centered complexes (1-3) are38-40nm red-shifted compared to those of the triphenylamine-centered complexes (4～6). The luminescence spectra of the complexes4-6in air-saturated chloroform showed two main emission peaks, in which the peak with shorter wavelength was ascribed to their fluorescence, and the peak with longer wavelength was ascribed to their phosphorescence. However, only the fluorescence has been detected for1～3in air-saturated chloroform. The molecular first order hyperpolarizabilities of the six target compounds were tested using solvatochromic method, and their molecular hyperpolarizabilities are in the range of4.06×10-29～2.11×10-28cm5/esu, which is much higher than that of some other common nonlinear optical materials. The results indicated that complexes2and5exhibit excellent nonlinear absorption properties. The ratios of the effective nonlinear absorption cross section to ground-state absorption cross section σeff/σ0of complexes1～6are in the range of4～22, aeffis far bigger than σ0, which indicates that this kind of compounds has the characteristics of the saturated absorption.
引文
[1]Parthenopoulos, D.A; Rentzepis, P.M. Three-Dimensional optical Storage memory. [J] Science 1989,245,843-845.
[2]Dvornikov, A.S.; Rentzepis, P.M. Accessing 3D memory information by means of nonlinear absorption. [J] Opt.Commum.1995,119,341-346.
[3]小泽哲磨.激光对人体的危害[J].应用物理,1992,61,949-952.
[4]Guo, F.; Kim, Y.G.; Reynolds, J. R.; et al. Platinum-acetylide polymer based solar cells: involvement of the triplet state for energy conversion. [J] Chem. Commun.2006,1887-1889
[5]将鸿旺.激光威胁,防护与对抗[J].光吃子技术与信息1992,3,5-9
[6]郭丰启.五氮齿金属配合物的合成、激发态性能研究及其在光限幅中的应用[D].[博士学术论文].北京：中国科学院感光化学研究所,2000.
[7]Chen, L.; Shelton, A.H.; Kye-Young, K.; et al. Organoplatinum chromophores for application in High-Performance nonlinear absorption materials. [J] ACS Appl. Mater. Interface 2011,3,3225-3238.
[8]Kim, H.; Cho, B. Two-photon materials with large two-photon cross sections. Structure-property relationship. [J] Chem. Commun.2009, (2),153-164.
[9]Lin, T.; Huang, Y.; Chen, Y.; et al. Two-photon absorption and effective broadband optical power limiting properties of a multi-branched chromophore containing 2,3-diarylquinoxalinyl moieties as the electron-pulling units. [J] Tetrahedron 2010,66, 1375-1382.
[10]Zhou, G; Wong, W.Y; Ye, C; et al. Optical power limiters based on colorless di-, oligo-, and polymetallaynes:Highly transparent materials for eye protection devices. [J] Adv. Func. Mater.2007,77,963-975.
[11]Su, X.; Xu, H.; Guo, Q.; et al. Stilbene-containing polyactylenes:Molecular design, synthesis, and relationship between molecular structure and NLO properties. [J] J. Polym. Sci. A:Polym. Chem.2008,46,4529-4541.
[12]崔浩.一种DMIT类金属有机配合物的光限幅特性的研究.[硕士学位论文].山东：山东大学,2010.
[13]范贺良.适用于全光于关的具有三阶非线性光学效应的DMIT材料聚合物复合薄膜的性能研究.[博士学位论文].山东：山东大学,2010.
[14]Bhawalhar, J.D.; He, G.S.; Prasad, P.N. Nonlinear multiphoton process in organic and polymeric materials [J]. Rep. Prog. Phys.1996,59,1041-1046.
[15]Tutt, L.W.; Boggess, T.F. A review of optical limiting mechanisms and devices using organics, fullerenes, semiconductors, and materials [J]. Prog. Quant. Electron 1993,17, 299-305.
[16]刘大军.反饱和吸收化合物制备及其激光防护光限幅性能的研究.[博士学位论文].长春：长春大学,2005.
[17]Hollins, R.C. Materials for optical limiters. [J] Curr. Opin. Solid State Mater. Sci.1999,4(2), 189-196.
[18]Yin, S.C.; Li, G; Xu, H.Y.; et al. Preparation and opical liming of a novel soluble phenylacetylene copolymer bearing nonlinear chromophoric pendants. [J] J. Funct. Mater. 2006,37(3,) 496-499.
[19]黄维.有机分子多光子吸收特性与其构型的关系的研究.[博士学位论文].南京：东南大学,2010.
[20]何国华.有机材料双光子吸收及光限幅特性的研究.[硕士学位论文].南京：东南大学,2004.
[21]陈煜.八-β-烷氧基酞菁及其金属配合物的线性和非线性光学特性[D].[硕士学术论文].北京：中国科学院化学研究所,2001.
[22]王芳芳.有机Π—电子共轭材料的线性与非线性光学性质研究.[硕士学位论文].河南：河南大学.2007.
[23]Chen, C.T.; Liu, L.Z. Nonlineare optical properties in inorganic materials. [J] Ann. Rev. Mater. Sci.1986,16,203-208.
[24]陈胜田.芳胺树状分子的制备与单/双光子性能研究.[硕士学位论文].南京：东南大学,2004
[25]Kurtz, S.K.; Perry, T.T. A powder technique for the evaluation of nonlinear optical materials. [J] J. Appl. Phys.1986,39,3798-3802.
[26]Jerphagnon, J.; Kurtz, S.K. Make fringes:A detailed comparison of theory and experiment for isotropic and uniaxial crystals. [J] J. Appl. Phys.1970,41,1667-1670.
[27]Williams, D.J. Nonlinear optical properties of organic and polymeric materials.vol.233 [M]. Amer Chemical Society,1985.
[28]Ulrick, U.R. Polymer of nonlinear optical applications[J]. Mol. Cryst. Liq.Cryst.1990, 1(189),3-38.
[29]Jenekhe, S.A.; Lo, S.K.; Flon, S.R. Nonlinear deoies using organometallic polymer. [J] Appl. Phys. Letts.1989,54,19-25.
[30]Dorsinville, R.; Yang, L.; Alfano, R.R. Measurement of the third order susciptibility in organic materials. [J] Opt. Letts.1989,14,23-28.
[31]Blau, W.; Burne, H.; Dennis, W.M. et al. Reverse saturable absorption in tetraphenylporphyrins. [J] Opt. Commun.1985,56,25-29.
[32]Rogers, J.E.; Cooper, T.M.; Fleitz, P.A.; et al. Photophysical characterization of a series of platinum (II)-containing phenyl-ethynyl oligomers. [J] J. Phys. Chem. A 2002,106(43), 10108-10115.
[33]Rogers, J.E.; Slagle, J.E.; Krein, D.M.; et al. Platinum acetylide two-photon chromophores. [J] Inorg. Chem.2007,46 (16),6483-94.
[34]Wilson, J.S.; Chawdhury, N.; Al-Mandhary, M. R. A.; et al. The energy gap law for triplet states in Pt-containing conjugated polymers and monomers. [J] J. Am. Chem. Soc.2001,123, (38),9412-9417.
[35]Rogers, J.E.; Hall, B.C.; Hufnagle, D.C.; et al. Effect of platinum on the photophysical properties of a series of phenyl-ethynyloligomers. [J] J. Chem. Phys.2005,122(21), 214708/1-8.
[36]Liu, Z.; Chen, T.; Liu, B.; et al. Two-photon absorption of a series of V-shape molecules:the influence of acceptor's strength on two-photon absorption in a noncentrosymmetric D-π-A-π-D system. [J] J. Mat. Chem.2007,17(44),4685-4689.
[37]Baur, J.W.; Alexander, M.D.Jr.; Banach, M.; et al. Molecular environment effects on two-photon-absorbing heterocyclic chromophores. [J] Chem. Mater.1999,11(10), 2899-2906.
[38]Yoon, K.R.; Sung, J.H.; Kim, D.; et al. Synthesis of new donor-fluorene-donor type organic dyes and their nonlinear absorption properties. [J] Opt. Mater.2007,29(11),1518-1522.
[39]Reinhardt, B.A.; Brott, L.L.; Clarson, S.J.; et al. Highly active two-photon dyes:design, synthesis, and characterization toward application. [J] Chem. Mater.1998,10(7), 1863-1874.
[40]Kannan, R.; He, G.S.; Yuan, L.; et al. Diphenylaminofluorene-based two-photon-absorbing chromophores with various π-electron acceptors. [J] Chem. Mater.2001,13(5), 1896-1904.
[41]Rodriguez, GJ.; Esquivias, J.; Lafuente, A.; et al. Synthesis of nanostructures based on 1, 4-and 1,3,5-ethynylphenyl subunits with π-extended conjugation, carbon dendron units. [J] J. Org. Chem.2003,68(21),8120-8128.
[42]Bruce, M.I.; Davy, J.; Hall, B.C.; et al. Some platinum (II) complexes derived from aromatic alkynes. [J] Appl. Organomet. Chem.2002,16(10),559-568.
[43]Hua, J.; Yang, W.; Zhu, Y.; et al. Optical-limiting effect of C60 bonded poly(N-vinylcarbazole) initiated with C60Cln/CuCl/Bpy catalyst system. [J] Mater. Lett. 2005,59(6),644-647.
[44]Sendhil, K.; Vijayan, C; Kothiyal, M.P. Low-threshold optical power limiting of cw laser illumination based on nonlinear refraction in zinc tetraphenyl porphyrin. [J] Opt. Laser Technol.2006,38 (7),512-515.
[45]Mishra, S.R.; Rawat, H.S.; Laghate, M. Nonlinear absorption and optical limiting in metalloporphyrins. [J] Opt. Commun.1998,147 (4-6),328-332.
[46]Powell, C.E.; Humphrey, M.G Nonlinear optical properties of transition metal acetylides and their derivatives. [J] Coord. Chem.Rev.2004,248(7-8),725-756.
[47]Li, C; Liu, C; Li, Q.; et al. Broad band optical limiting and nonlinear optical absorption properties of a novel hyperbranched conjugated polymer. [J] Chem. Phys. Lett.2004, 400(4-6),569-572.
[48]Lin, T.C.; He, GS.; Zheng, Q.; et al. Degenerate two-/three-photon absorption and optical power-limiting properties in femtosecond regime of a multi-branched chromophore. [J] J. Mater. Chem.2006,16 (25),2490-2498.
[49]Varnavski, O.; Yan, X.; Mongin, O.; et al. Strongly interacting organic conjugated dendrimers with enhanced two-photon absorption. [J] J. Phys. Chem. C 2007,111(1), 149-162.
[50]Samoc, M.; Morrall, J.P.; Dalton, G.T.; et al. Two-photon and three-photon absorption in an organometallic dendrimer. [J] Angew. Chem. Int. Ed.2007,46(5),731-733.
[51]Chawdhury, N.;Koehler, A.; Friend, R.H.; et al. Synthesis and electronic structure of platinum-containing poly-ynes with aromatic and heteroaromatic rings. [J] Macromolecules 1998,31(3),722-727.
[52]Brabec, C.J.; Sariciftci, N.S.; Hummelen, J.C. A low-bandgap semiconducting polymer for photovoltaic devices and infrared emitting diodes [J]. Adv. Fund Mater.2002,10,709-712.
[53]Brabec, C.J. Organic photovoltaics:Technology and market. [J] Sol. Energy Mater. Sol. Cells,2004,83,273-292.
[54]Sariciftci, N.S.; Braun, D.; Zhang, C; et al. Semiconducting polymer-buckminster fullerene heterojunctions:Diodes, photodiodes, and photovoltaic cells. [J] Appl. Phys. Lett,1993,62: 585-587.
[55]Li, G; Shrotriya, V.; Huang, J.S.; et al. High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends. [J] Nat. Mater,2005,4(11), 864-868.
[56]Al-Ibrahim, M.; Sensfuss, S.; Uziel, J.; et al. Comparison of normal and inverse poly(3-hexylthiophene)/fullerene solar cell architectures. [J] Sol. Energy Mater. Sol. Cells, 2005,55,277-283.
[57]Kroon, J.M.; Wienk, M.M.; Verhees, W.J.H.; et al. Accurate efficiency determination and stability studies of conjugated polymer/fullerene solar cells. [J] Thin Solid Films,2002, 403-404.
[58]Zhang, J.; Xu, X.; Chen, L.; et al. Platinum acetylide complexes containing lptycene as cores:a new ffmily of unexpected efficient organometallic gelators. [J] Organometallics 2011,30,4032-4038.
[59]Thomas, M.C.; Douglas, M.K.; Aarom, R.B.; et al. Spectroscopic structure-property relationships of a series of polyaromtic platinum acetylides. [J] J. Phys. Chem. A 2012,116, 139-149.
[60]Nguyen, M.; John, H.K.Y. Platinum-conjugated HOMO-and heterobichromophoric complexes of tetracene and pentacene. [J] Organometallics 2012,31,7522-7531.
[61]Denis, C.; Frederic, C.; Cesar, L.; et al. Silica hybrid sol-gel materials with unusually high concentration of Pt-organic molecular guests:studies of luminescence and nonlinear absorption of light [J] ACS Appl. Mater. Interfaes 2012,4,2369-2377.
[62]Swarup, K.M.; Manuel, G.J.; Joao, R. Divergent Route to the Preparation of Hybrid Pt-Fe 2,4.6-Tris(4-ethynyl)phenyl-l,3,5-triazine Metallodendrimers for Nonlinear Optics. [J] Organometallics 2013,32,406-414.
[63]Guo, F.; Ogawa, K.; Kim, Y. A fulleopyrrolidine end-capped platinum-acetylide triad:the mechanism of photoinduecd charge transfer in organometallic photovoltaic cells. [J] Phys. Chem. Chem. Phys.2007,9,2724-2734.
[64]Kwok, C.C.; Ngai, H.M.Y.; Chan, S.C.; et al. [(OANAN)PtX] Complexes as a new class of light-emitting materials for electrophosphorescent devices. [J] Inorg. Chem.2005,44, 4442-4444.
[65]McGarrah, J.E.; Eisenberg, R. Dyads for photoinduced charge separation based on platinum diimine bis(acetylide) chromophores:Synthesis,luminescence and transient absorption studies. [J] Inorg. Chem.2003,42,4355-4365.
[66]买丽丹·吾马尔.芳炔类共轭聚合物的合成及发到能研究.[硕士学位论文].新疆：新疆大学,2009.
[67]柯城,唐星华,吴雪梅.Sonogashira反应机理研究进展.[J]江西科学,2008,26(3),426-429.
[68]Sonogashira, K.; Fujikura, Y.; Yatake, T.; et al. Syntheses and properties of cis-and trans-dialkynyl complexes of platinum (II). [J] J. Organomet. Chem.1978,145,101-108.
[69]Chen, L.; James, E.Y.; Ksenija, D.G.; et al. Photoinduced charge separation in platinum acetylide oligomers. [J] J. Phys. Chem. B 2010,114,14763-14771.
[70]Schaefer, F.C.; Peters, G.A. Synthesis of the s-triazine system. III, Trimerization of imidates. [J] J. Org. Chem.,1961,26,2778-2784.
[71]Teng, C; Yang, X.; Yang, C; et al. Molecular design of anthracene-bridged metal-free organic dyes for efficient dye-sensitized solar cells. [J] J. Phys. Chem. C 2010,114, 9101-9110.
[72]Zhang, H.X.; Gao, S.; Yang, X.X. Synthesis of an octupolar compound and its biological effects on serum albumin. [J] Mol. Biol. Rep.2009,36,1405-1411.
[73]韩元元.含重金属芳香炔类低聚物的合成和表征[D].[硕士学术论文].郑州：郑州大学,2010.
[74]王海萍.含重金属离子的芳香炔类共轭低聚物的合成与表征[D].[硕士学术论文].郑州：郑州大学,2011.
[75]Crosby, G.A.; Demas, J.N. The measurement of photoluminescence quantum yields. [J] J. Phys. Chem.1971,75,991-1024.
[76]Van-Houten, J.; Watts, R.J. Temperature dependence of the photophysical and photochemical properties of the Tris(2,2'-bipyridyl)ruthenium(II)ion in aqueous solution. [J] J. Am. Chem. Soc.1976,98,4853-4858.
[77]Chen, L.; Shelton, A.H.; Kim, K.; et al. Organoplatinum chromophores for application in High-Performance nonlinear absorption materials. [J] ACS Appl. Mater. Interface 2011,3, 3225-3238.
[78]Paley, M.S.; Harris, J.M.; Looser, H.; et al. Solvatochromic method for determining second-order polarizabilities of organic molecules. [J] J. Org. Chem.1989,54,3774-3778.
[79]Deguan, L.; Ratner, M.A.; Marks, T.J. Molecular and macromolecular nonlinear optical materials. Probing architecture/electronic structure/frequency doubling relationships via an SCF-LCAO MECI n electron formalism. [J] J. Am. Chem. Soc.1988,110,1707-1715.
[80]Liptay, W. Electrochromism and Solvatochromism. [J] Angew. Chem, Int. Ed Engl.1969,8, 177-188.
[81]Hillebrand, S.; Segala, M.; Buckup, T; et al. First hyperpolarizability in proton-transfer benzoxazoles:computer-aided design, synthesis and study of a new model compound. [J] Chem. Phys.2001,273,1-10.
[82]Chemla, D.S.; Zyss, J. Ed., Nonlinear optical properties of organic molecules and crystals.vol.land 2[M].Academic Press, New York,1987.
[83]Toro, C; Hinchliffe, A.; Arrieta, F.; et al. Structural and dipole (hyper)polarizabilities of the ground and excited singlet states of urea and thiourea:A gas phase CIS(D) theoretical study. [J] J. Comput. Methods. Sci.Eng.2009,9,289-300.
[84]Zhan, C; Wang, D. Solvent effects on molecular first-hyperpolarizabilities of stilbazolium-like dyes. [J]化学学报2000,58(1),24-28.
[85]Sheik-Bahae, M.; Said, A.A.; Van-Stryland, E.W. High-sensitivity, single-beam n2 measurements. [J] Opt. Lett.1989,14,955-957.
[86]Wood, GL.; Miller. M.J.; Mott, A.G Investigation of tetrabenzporphyrin by the Z-scan technique. [J] Opt. Lett.1955,20,973-979.
[87]陈煜,李去静,聂玉昕.8-辛烷氧基金属酞菁的皮秒三阶光学非线性与光限幅特性.[J]物理学报,2002,51(3),578-583.
[88]Xia, T.J.; Hagan, D.J.; Dogariu, A.; et al. Optimization of optical limiting devices based on excited-state absorption. [J] Appl. Opt.1997,36,4110-4122.
[89]Perry, J.W.; Mansour, K.; Marder, S.R.; et al. Enhanced reverse saturable absorption and optical limiting in heavy-atom-substituted phthalocyanines. [J] Opt. Lett.1994,19(9) 625-627.
[90]Li, Y.J.; Pritchett, T.M.; Huang, J.D.; et al. Photophysics and nonlinear absorption of peripheral-substituted zinc phthalocyanines. [J] J. Phys. Chem. A 2008,112,7200-7207.
[91]Gopper-mayer,M. Uber Elementarakte mit zwei Quantensprungen. [J] Ann. Phs. Lpz. 1931,3,273-294.
[2]Dvornikov, A.S.; Rentzepis, P.M. Accessing 3D memory information by means of nonlinear absorption. [J] Opt.Commum.1995,119,341-346.
[3]小泽哲磨.激光对人体的危害[J].应用物理,1992,61,949-952.
[4]Guo, F.; Kim, Y.G.; Reynolds, J. R.; et al. Platinum-acetylide polymer based solar cells: involvement of the triplet state for energy conversion. [J] Chem. Commun.2006,1887-1889
[5]将鸿旺.激光威胁,防护与对抗[J].光吃子技术与信息1992,3,5-9
[6]郭丰启.五氮齿金属配合物的合成、激发态性能研究及其在光限幅中的应用[D].[博士学术论文].北京：中国科学院感光化学研究所,2000.
[7]Chen, L.; Shelton, A.H.; Kye-Young, K.; et al. Organoplatinum chromophores for application in High-Performance nonlinear absorption materials. [J] ACS Appl. Mater. Interface 2011,3,3225-3238.
[8]Kim, H.; Cho, B. Two-photon materials with large two-photon cross sections. Structure-property relationship. [J] Chem. Commun.2009, (2),153-164.
[9]Lin, T.; Huang, Y.; Chen, Y.; et al. Two-photon absorption and effective broadband optical power limiting properties of a multi-branched chromophore containing 2,3-diarylquinoxalinyl moieties as the electron-pulling units. [J] Tetrahedron 2010,66, 1375-1382.
[10]Zhou, G; Wong, W.Y; Ye, C; et al. Optical power limiters based on colorless di-, oligo-, and polymetallaynes:Highly transparent materials for eye protection devices. [J] Adv. Func. Mater.2007,77,963-975.
[11]Su, X.; Xu, H.; Guo, Q.; et al. Stilbene-containing polyactylenes:Molecular design, synthesis, and relationship between molecular structure and NLO properties. [J] J. Polym. Sci. A:Polym. Chem.2008,46,4529-4541.
[12]崔浩.一种DMIT类金属有机配合物的光限幅特性的研究.[硕士学位论文].山东：山东大学,2010.
[13]范贺良.适用于全光于关的具有三阶非线性光学效应的DMIT材料聚合物复合薄膜的性能研究.[博士学位论文].山东：山东大学,2010.
[14]Bhawalhar, J.D.; He, G.S.; Prasad, P.N. Nonlinear multiphoton process in organic and polymeric materials [J]. Rep. Prog. Phys.1996,59,1041-1046.
[15]Tutt, L.W.; Boggess, T.F. A review of optical limiting mechanisms and devices using organics, fullerenes, semiconductors, and materials [J]. Prog. Quant. Electron 1993,17, 299-305.
[16]刘大军.反饱和吸收化合物制备及其激光防护光限幅性能的研究.[博士学位论文].长春：长春大学,2005.
[17]Hollins, R.C. Materials for optical limiters. [J] Curr. Opin. Solid State Mater. Sci.1999,4(2), 189-196.
[18]Yin, S.C.; Li, G; Xu, H.Y.; et al. Preparation and opical liming of a novel soluble phenylacetylene copolymer bearing nonlinear chromophoric pendants. [J] J. Funct. Mater. 2006,37(3,) 496-499.
[19]黄维.有机分子多光子吸收特性与其构型的关系的研究.[博士学位论文].南京：东南大学,2010.
[20]何国华.有机材料双光子吸收及光限幅特性的研究.[硕士学位论文].南京：东南大学,2004.
[21]陈煜.八-β-烷氧基酞菁及其金属配合物的线性和非线性光学特性[D].[硕士学术论文].北京：中国科学院化学研究所,2001.
[22]王芳芳.有机Π—电子共轭材料的线性与非线性光学性质研究.[硕士学位论文].河南：河南大学.2007.
[23]Chen, C.T.; Liu, L.Z. Nonlineare optical properties in inorganic materials. [J] Ann. Rev. Mater. Sci.1986,16,203-208.
[24]陈胜田.芳胺树状分子的制备与单/双光子性能研究.[硕士学位论文].南京：东南大学,2004
[25]Kurtz, S.K.; Perry, T.T. A powder technique for the evaluation of nonlinear optical materials. [J] J. Appl. Phys.1986,39,3798-3802.
[26]Jerphagnon, J.; Kurtz, S.K. Make fringes:A detailed comparison of theory and experiment for isotropic and uniaxial crystals. [J] J. Appl. Phys.1970,41,1667-1670.
[27]Williams, D.J. Nonlinear optical properties of organic and polymeric materials.vol.233 [M]. Amer Chemical Society,1985.
[28]Ulrick, U.R. Polymer of nonlinear optical applications[J]. Mol. Cryst. Liq.Cryst.1990, 1(189),3-38.
[29]Jenekhe, S.A.; Lo, S.K.; Flon, S.R. Nonlinear deoies using organometallic polymer. [J] Appl. Phys. Letts.1989,54,19-25.
[30]Dorsinville, R.; Yang, L.; Alfano, R.R. Measurement of the third order susciptibility in organic materials. [J] Opt. Letts.1989,14,23-28.
[31]Blau, W.; Burne, H.; Dennis, W.M. et al. Reverse saturable absorption in tetraphenylporphyrins. [J] Opt. Commun.1985,56,25-29.
[32]Rogers, J.E.; Cooper, T.M.; Fleitz, P.A.; et al. Photophysical characterization of a series of platinum (II)-containing phenyl-ethynyl oligomers. [J] J. Phys. Chem. A 2002,106(43), 10108-10115.
[33]Rogers, J.E.; Slagle, J.E.; Krein, D.M.; et al. Platinum acetylide two-photon chromophores. [J] Inorg. Chem.2007,46 (16),6483-94.
[34]Wilson, J.S.; Chawdhury, N.; Al-Mandhary, M. R. A.; et al. The energy gap law for triplet states in Pt-containing conjugated polymers and monomers. [J] J. Am. Chem. Soc.2001,123, (38),9412-9417.
[35]Rogers, J.E.; Hall, B.C.; Hufnagle, D.C.; et al. Effect of platinum on the photophysical properties of a series of phenyl-ethynyloligomers. [J] J. Chem. Phys.2005,122(21), 214708/1-8.
[36]Liu, Z.; Chen, T.; Liu, B.; et al. Two-photon absorption of a series of V-shape molecules:the influence of acceptor's strength on two-photon absorption in a noncentrosymmetric D-π-A-π-D system. [J] J. Mat. Chem.2007,17(44),4685-4689.
[37]Baur, J.W.; Alexander, M.D.Jr.; Banach, M.; et al. Molecular environment effects on two-photon-absorbing heterocyclic chromophores. [J] Chem. Mater.1999,11(10), 2899-2906.
[38]Yoon, K.R.; Sung, J.H.; Kim, D.; et al. Synthesis of new donor-fluorene-donor type organic dyes and their nonlinear absorption properties. [J] Opt. Mater.2007,29(11),1518-1522.
[39]Reinhardt, B.A.; Brott, L.L.; Clarson, S.J.; et al. Highly active two-photon dyes:design, synthesis, and characterization toward application. [J] Chem. Mater.1998,10(7), 1863-1874.
[40]Kannan, R.; He, G.S.; Yuan, L.; et al. Diphenylaminofluorene-based two-photon-absorbing chromophores with various π-electron acceptors. [J] Chem. Mater.2001,13(5), 1896-1904.
[41]Rodriguez, GJ.; Esquivias, J.; Lafuente, A.; et al. Synthesis of nanostructures based on 1, 4-and 1,3,5-ethynylphenyl subunits with π-extended conjugation, carbon dendron units. [J] J. Org. Chem.2003,68(21),8120-8128.
[42]Bruce, M.I.; Davy, J.; Hall, B.C.; et al. Some platinum (II) complexes derived from aromatic alkynes. [J] Appl. Organomet. Chem.2002,16(10),559-568.
[43]Hua, J.; Yang, W.; Zhu, Y.; et al. Optical-limiting effect of C60 bonded poly(N-vinylcarbazole) initiated with C60Cln/CuCl/Bpy catalyst system. [J] Mater. Lett. 2005,59(6),644-647.
[44]Sendhil, K.; Vijayan, C; Kothiyal, M.P. Low-threshold optical power limiting of cw laser illumination based on nonlinear refraction in zinc tetraphenyl porphyrin. [J] Opt. Laser Technol.2006,38 (7),512-515.
[45]Mishra, S.R.; Rawat, H.S.; Laghate, M. Nonlinear absorption and optical limiting in metalloporphyrins. [J] Opt. Commun.1998,147 (4-6),328-332.
[46]Powell, C.E.; Humphrey, M.G Nonlinear optical properties of transition metal acetylides and their derivatives. [J] Coord. Chem.Rev.2004,248(7-8),725-756.
[47]Li, C; Liu, C; Li, Q.; et al. Broad band optical limiting and nonlinear optical absorption properties of a novel hyperbranched conjugated polymer. [J] Chem. Phys. Lett.2004, 400(4-6),569-572.
[48]Lin, T.C.; He, GS.; Zheng, Q.; et al. Degenerate two-/three-photon absorption and optical power-limiting properties in femtosecond regime of a multi-branched chromophore. [J] J. Mater. Chem.2006,16 (25),2490-2498.
[49]Varnavski, O.; Yan, X.; Mongin, O.; et al. Strongly interacting organic conjugated dendrimers with enhanced two-photon absorption. [J] J. Phys. Chem. C 2007,111(1), 149-162.
[50]Samoc, M.; Morrall, J.P.; Dalton, G.T.; et al. Two-photon and three-photon absorption in an organometallic dendrimer. [J] Angew. Chem. Int. Ed.2007,46(5),731-733.
[51]Chawdhury, N.;Koehler, A.; Friend, R.H.; et al. Synthesis and electronic structure of platinum-containing poly-ynes with aromatic and heteroaromatic rings. [J] Macromolecules 1998,31(3),722-727.
[52]Brabec, C.J.; Sariciftci, N.S.; Hummelen, J.C. A low-bandgap semiconducting polymer for photovoltaic devices and infrared emitting diodes [J]. Adv. Fund Mater.2002,10,709-712.
[53]Brabec, C.J. Organic photovoltaics:Technology and market. [J] Sol. Energy Mater. Sol. Cells,2004,83,273-292.
[54]Sariciftci, N.S.; Braun, D.; Zhang, C; et al. Semiconducting polymer-buckminster fullerene heterojunctions:Diodes, photodiodes, and photovoltaic cells. [J] Appl. Phys. Lett,1993,62: 585-587.
[55]Li, G; Shrotriya, V.; Huang, J.S.; et al. High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends. [J] Nat. Mater,2005,4(11), 864-868.
[56]Al-Ibrahim, M.; Sensfuss, S.; Uziel, J.; et al. Comparison of normal and inverse poly(3-hexylthiophene)/fullerene solar cell architectures. [J] Sol. Energy Mater. Sol. Cells, 2005,55,277-283.
[57]Kroon, J.M.; Wienk, M.M.; Verhees, W.J.H.; et al. Accurate efficiency determination and stability studies of conjugated polymer/fullerene solar cells. [J] Thin Solid Films,2002, 403-404.
[58]Zhang, J.; Xu, X.; Chen, L.; et al. Platinum acetylide complexes containing lptycene as cores:a new ffmily of unexpected efficient organometallic gelators. [J] Organometallics 2011,30,4032-4038.
[59]Thomas, M.C.; Douglas, M.K.; Aarom, R.B.; et al. Spectroscopic structure-property relationships of a series of polyaromtic platinum acetylides. [J] J. Phys. Chem. A 2012,116, 139-149.
[60]Nguyen, M.; John, H.K.Y. Platinum-conjugated HOMO-and heterobichromophoric complexes of tetracene and pentacene. [J] Organometallics 2012,31,7522-7531.
[61]Denis, C.; Frederic, C.; Cesar, L.; et al. Silica hybrid sol-gel materials with unusually high concentration of Pt-organic molecular guests:studies of luminescence and nonlinear absorption of light [J] ACS Appl. Mater. Interfaes 2012,4,2369-2377.
[62]Swarup, K.M.; Manuel, G.J.; Joao, R. Divergent Route to the Preparation of Hybrid Pt-Fe 2,4.6-Tris(4-ethynyl)phenyl-l,3,5-triazine Metallodendrimers for Nonlinear Optics. [J] Organometallics 2013,32,406-414.
[63]Guo, F.; Ogawa, K.; Kim, Y. A fulleopyrrolidine end-capped platinum-acetylide triad:the mechanism of photoinduecd charge transfer in organometallic photovoltaic cells. [J] Phys. Chem. Chem. Phys.2007,9,2724-2734.
[64]Kwok, C.C.; Ngai, H.M.Y.; Chan, S.C.; et al. [(OANAN)PtX] Complexes as a new class of light-emitting materials for electrophosphorescent devices. [J] Inorg. Chem.2005,44, 4442-4444.
[65]McGarrah, J.E.; Eisenberg, R. Dyads for photoinduced charge separation based on platinum diimine bis(acetylide) chromophores:Synthesis,luminescence and transient absorption studies. [J] Inorg. Chem.2003,42,4355-4365.
[66]买丽丹·吾马尔.芳炔类共轭聚合物的合成及发到能研究.[硕士学位论文].新疆：新疆大学,2009.
[67]柯城,唐星华,吴雪梅.Sonogashira反应机理研究进展.[J]江西科学,2008,26(3),426-429.
[68]Sonogashira, K.; Fujikura, Y.; Yatake, T.; et al. Syntheses and properties of cis-and trans-dialkynyl complexes of platinum (II). [J] J. Organomet. Chem.1978,145,101-108.
[69]Chen, L.; James, E.Y.; Ksenija, D.G.; et al. Photoinduced charge separation in platinum acetylide oligomers. [J] J. Phys. Chem. B 2010,114,14763-14771.
[70]Schaefer, F.C.; Peters, G.A. Synthesis of the s-triazine system. III, Trimerization of imidates. [J] J. Org. Chem.,1961,26,2778-2784.
[71]Teng, C; Yang, X.; Yang, C; et al. Molecular design of anthracene-bridged metal-free organic dyes for efficient dye-sensitized solar cells. [J] J. Phys. Chem. C 2010,114, 9101-9110.
[72]Zhang, H.X.; Gao, S.; Yang, X.X. Synthesis of an octupolar compound and its biological effects on serum albumin. [J] Mol. Biol. Rep.2009,36,1405-1411.
[73]韩元元.含重金属芳香炔类低聚物的合成和表征[D].[硕士学术论文].郑州：郑州大学,2010.
[74]王海萍.含重金属离子的芳香炔类共轭低聚物的合成与表征[D].[硕士学术论文].郑州：郑州大学,2011.
[75]Crosby, G.A.; Demas, J.N. The measurement of photoluminescence quantum yields. [J] J. Phys. Chem.1971,75,991-1024.
[76]Van-Houten, J.; Watts, R.J. Temperature dependence of the photophysical and photochemical properties of the Tris(2,2'-bipyridyl)ruthenium(II)ion in aqueous solution. [J] J. Am. Chem. Soc.1976,98,4853-4858.
[77]Chen, L.; Shelton, A.H.; Kim, K.; et al. Organoplatinum chromophores for application in High-Performance nonlinear absorption materials. [J] ACS Appl. Mater. Interface 2011,3, 3225-3238.
[78]Paley, M.S.; Harris, J.M.; Looser, H.; et al. Solvatochromic method for determining second-order polarizabilities of organic molecules. [J] J. Org. Chem.1989,54,3774-3778.
[79]Deguan, L.; Ratner, M.A.; Marks, T.J. Molecular and macromolecular nonlinear optical materials. Probing architecture/electronic structure/frequency doubling relationships via an SCF-LCAO MECI n electron formalism. [J] J. Am. Chem. Soc.1988,110,1707-1715.
[80]Liptay, W. Electrochromism and Solvatochromism. [J] Angew. Chem, Int. Ed Engl.1969,8, 177-188.
[81]Hillebrand, S.; Segala, M.; Buckup, T; et al. First hyperpolarizability in proton-transfer benzoxazoles:computer-aided design, synthesis and study of a new model compound. [J] Chem. Phys.2001,273,1-10.
[82]Chemla, D.S.; Zyss, J. Ed., Nonlinear optical properties of organic molecules and crystals.vol.land 2[M].Academic Press, New York,1987.
[83]Toro, C; Hinchliffe, A.; Arrieta, F.; et al. Structural and dipole (hyper)polarizabilities of the ground and excited singlet states of urea and thiourea:A gas phase CIS(D) theoretical study. [J] J. Comput. Methods. Sci.Eng.2009,9,289-300.
[84]Zhan, C; Wang, D. Solvent effects on molecular first-hyperpolarizabilities of stilbazolium-like dyes. [J]化学学报2000,58(1),24-28.
[85]Sheik-Bahae, M.; Said, A.A.; Van-Stryland, E.W. High-sensitivity, single-beam n2 measurements. [J] Opt. Lett.1989,14,955-957.
[86]Wood, GL.; Miller. M.J.; Mott, A.G Investigation of tetrabenzporphyrin by the Z-scan technique. [J] Opt. Lett.1955,20,973-979.
[87]陈煜,李去静,聂玉昕.8-辛烷氧基金属酞菁的皮秒三阶光学非线性与光限幅特性.[J]物理学报,2002,51(3),578-583.
[88]Xia, T.J.; Hagan, D.J.; Dogariu, A.; et al. Optimization of optical limiting devices based on excited-state absorption. [J] Appl. Opt.1997,36,4110-4122.
[89]Perry, J.W.; Mansour, K.; Marder, S.R.; et al. Enhanced reverse saturable absorption and optical limiting in heavy-atom-substituted phthalocyanines. [J] Opt. Lett.1994,19(9) 625-627.
[90]Li, Y.J.; Pritchett, T.M.; Huang, J.D.; et al. Photophysics and nonlinear absorption of peripheral-substituted zinc phthalocyanines. [J] J. Phys. Chem. A 2008,112,7200-7207.
[91]Gopper-mayer,M. Uber Elementarakte mit zwei Quantensprungen. [J] Ann. Phs. Lpz. 1931,3,273-294.