三、本书主要内容

如前所述，金属-有机配合物是无机和有机化合物的相互结合的产物，它集中了无机物和有机物两方面的优越性：优良的物化稳定性、宽的透光波段和易于分子设计、高的非线性光学系数。因此，这类化合物在非线性光学材料研究中占据重要地位。目前国内外有许多这类材料和晶体的报道，所用配体包括硫氰酸根[91～93]、硫脲及其衍生物类[94～100]、冠醚类[101，102]、吡啶羧酸类[103～113]和氨基酸及其衍生物类[114～121]等等，所报道的配合物材料大多具有较好的粉末倍频效应，而且透光波段能到达紫外区，在二阶非线性光学材料领域展示了良好的应用前景。在所报道的金属-有机配合物中，中心金属一般都选择ⅡB族金属，因为ⅡB族金属在其形成的金属有机配合物中，以二价离子存在，最外层特征电子构型为d轨道满壳层，不存在d-d跃迁，与一般配体形成的配合物一般为无色晶体，在紫外、可见和近红外都有较好的透光性能[122]。因此，有关这类配合物作为倍频材料的研究非常多见。

本书以一些简单的配体作为起始原料，在温和条件下，设计、合成各种金属配合物，测定晶体结构，并积极开展了一些相关的物理化学性质的研究，努力揭示晶体结构与其二阶非线性光学效应之间的新现象，新问题，为进一步拓展和深化该工作奠定基础。

主要内容分为以下几部分。

（1）将TPPO引入到二阶非线性光学材料的研究当中。以TPPO为配体，合成了一系列ⅡB族金属与TPPO的配合物，测定了晶体结构，并对其粉末倍频效应进行了测试研究。对其中粉末倍频效应比较好的配合物Zn（TPPO）2Cl2生长出了大单晶，测得了其转换效率以及光损伤阈值。

（2）将共轭配体NCS-引入TPPO与ⅡB族金属离子体系中，在温和条件下合成了一系列ⅡB族金属与配体TPPO以及NCS-的配合物，测定了晶体结构，并对其粉末倍频效应进行了测试研究。

（3）合成了对氨基苯甲酸为配体的配位聚合物。并对其粉末倍频效应以及其他光学性质和物化性质进行了测试研究。研究证明了配位聚合物结构中的氢键对其非线性光学效应有很大影响。

（4）设计并合成了一系列TPPO与镧系元素的配合物，其结构为中心对称，故没有倍频效应。

参考文献

[1]叶成.分子非线性光学材料研究的新进展[J].光电子·激光，1996，7（2）：69-76

[2]S.R.Marder,B.Kippelen,A.K.Y.Jen,N.Peyghambarian,Design and synthesis of chromophores and polymers for electro-optic and photorefractive applications[J]，Nature，1997，388：845-851

[3]张克从，王希敏.非线性光学晶体材料科学.科学出版社，1996

[4]吴以成，陈创天.使用基团理论计算KB5O8·4H2O晶体的倍频系数[J].物理学报，1986，35：1-6

[5]A.Lago,R.Wallenstein,C.Chen,Y.X.Fan,R.L.Byer,Coherent 70.9nm radiation generated in neon by frequency tripling the fifth harmonic of a Nd：YAG laser[J]，Optics Letters 1988，13：221-223

[6]N.Zhang,M.H.Jiang,D.R.Yuan,D.Xu,X.T.Tao,Z.S.Shao,The quality and performance of the organometallic complex nonlinear optical material tri-allylthiourea cadmium chloride（ATCC）[J]，J.Cryst.Growth 1990，102：581-584

[7]V.Venkataramanan,G.Dhanaraj,V.K.Wadhawan,J.N.Shrewood,H.L.Bhat,Crystal growth and defects characterization of zinc tris（thiourea）sulfate：a novel metalorganic nonlinear optical crystal[J]，J.Cryst.Growth 1995，154：92-97

[8]P.M.Ushasree,R.Muralidharan,R.Jayavel,P.Ramasamy,Growth of bis（thiourea）cadmium chloride single crystals-a potential NLO material of organometallic complex[J]，J.Cryst.Growth 2000，218：365-371

[9]H.O.Marcy,C.F.Warren,M.S.Webb,C.A.Ebbers,S.P.Velsko,G.C.Kennedy,G.C.Catella,Second-harmonic generation in zinc tris（thiourea）sulfate[J]，Appl.Opt.1992，31：5051-5060

[10]K.Selvaraju,R.Valluvan,S.Kumararaman,Growth and characterization of a new metal-organic crystal：Potassium thiourea iodide[J]，Mater.Lett.2006，60：3130-3132

[11]K.Selvaraju,R.Valluvan,S.Kumararaman,A new metal-organic crystal：Potassium thiourea chloride[J]，Mater.Lett.2007，61：751-754

[12]V.Venkataramanan,C.K.Subramanian,H.L.Bhat,Laser induced damage in zinc tris（thiourea）sulfate and bis（thiourea）cadmium chloride[J]，J.Appl.Phys.1995，77：6049-6051

[13]R.Rajasekaran,P.M.Ushasree,R.Jayavel,P.Ramasamy,Growth and characterization of zinc thiourea chloride（ZTC）：a semiorganic nonlinear optical crystal[J]，J.Cryst.Growth 2001，229：563-567

[14]K.Rajarajan,S.Selvakumar,G.P.Joseph,I.V.Potheher,M.G.Mohamed,P.Sagayaraj,Growth,dielectric and photoconducting studies of tetrathiourea mercury（II）tetrathiocyanato zinc（II）NLO single crystals[J]，Journal of Crystal Growth 2006，286：470-475

[15]S.Selvakumar,S.M.R.Kumar,K.Rajarajan,A.J.A.Pragasam,S.A.Rajasekar,K.Thamizharasan,P.Sagayaraj,Growth and Characterization of a Novel Organometallic Nonlinear Optical Crystal：Bis（Thiourea）Cadmium Formate[J]，Cryst.Growth＆Design 2006，6：2607-2610

[16]卢绍芳，何美云，黄金陵.偏硼酸钡低温相的晶体结构[J].物理学报，1982，31（7）：948-955

[17]S.Lin,Z.Sun,B.Wu,C.Chen.The nonlinear optical characteristics of a LiB3O5 crystal[J]，J.Appl.Phys.1990，67：634-638

[18]洪海平，王业斌，林绮，周淑琴，金祥凤.无机非线性材料的探索[J].化学通报，1994，10：18-20

[19]（a）H.Jiang,D.Li,K.Zhang,H.Liu,J.Wang,Optical and thermal properties of nonlinear optical crystal LaCa4O（BO3）3[J]，Chemical Physics Letters 2003，372：788-793

[20]J.J.Adams,C.A.Ebbers,K.I.Schaffers,S.A.Payne,Nonlinear optical properties of LaCa4O（BO3）3[J]，Opt.Lett.2001，26：217-219

[21]S.Yang,G.Li,S.Tian,F.Liao,J.Lin,Synthesis and Structure of[C2H10N2][B5O8（OH）]：A Nonmetal Pentaborate with Nonlinear Optical Properties[J]，Crystal Growth＆Design 2007，7：1246-1250

[22]F.Kong,S.Huang,Z.Sun,J.Mao,W.Cheng,Se2（B2O7）：A New Type of Second-Order NLO Material[J]，J.Am.Chem.Soc.2006，128：7750-7751

[23]K.Xu,P.Loiseau,Growth and characterization of a nonlinear borate optical crystal：BaNaB9O15[J]，Journal of Crystal Growth 2009，311：389-393

[24]N.Ye,D.Tang,Hydrothermal growth of KBe2BO3F2 crystals[J]，Journal of Crystal Growth 2006，293：233-235

[25]H.X.Chen,N.Zhuang,R.Wang,J.Chen.Growth,nonlinear frequency-doubling and spectral properties of Nd：Ca8.53K1.09La0.95（VO4）7 crystal[J].Journal of Crystal Growth 2008，310：5423-5427

[26]L.Gheorghe,P.Loiseau,G.Aka,V.Lupei,Growth and type-I noncritical phase-matching second-harmonic generation of Gd1-XRxCa4O（BO3）3（R 3+=Sc 3+or Lu 3+）crystals[J].Journal of Crystal Growth 2006，294：442-446

[27]V.T.Adamiv,Y.V.Burak,I.M.Teslyuk.Growth and properties of new nonlinear LiKB4O7 single crystals[J].Journal of Crystal Growth 2006，289：157-160

[28]F.Zhang,D.Shen,G.Shen,X.Wang,Growth and characterization of non-linear optical crystal Cd3Zn3B4O12[J]，Materials Research Bulletin 2008，43：3188-3194

[29]G.Chen,Y.Wu,P.Fu,Growth and characterization of a new nonlinear optical crystal Ca5（BO3）3F[J]，Journal of Crystal Growth 2006，292：449-453

[30]P.R.Varanasi,A.K.Jen,J.Chandrasekhar,I.N.N.Namboothiri,A.Rathna,The Important Role of Heteroaromatics in the Design of Efficient Second-Order Nonlinear Optical Molecules：Theoretical Investigation on Push-Pull Heteroaromatic Stilbenes[J]，J.Am.Chem.Soc.1996，118：12443-12448

[31]S.B.Monaco,L.E.Davis,S.P.Velsko,F.T.Wng,D.Eimerl,Synthesis and characterization of chemical analogs of L-arginine phosphate[J]，J.Crystal Growth 1987，85：252-255

[32]G.Dhanraj,T.Shripathi,H.L.Bhat,Growth and defect characterization of L-arginine phosphate monohydrate[J]，J.Crystal Growth 1991，113：456-464

[33]H.O.Marcy,M.J.Rosker,L.F.Warren,P.H.Cunningham,C.A.Thomas,L.A.Deloach,S.P.Velsko,L.A.Ebbers,J.H.Liao,M.G.Kanatzidis,L-Histidine tetrafluoroborate：a solution-grown semiorganic crystal for nonlinear frequency conversion[J]，Opt.Lett.1995，20：252-254

[34]M.D.Agarwal,J.Choi,W.S.Wang,K.Bhat,R.B.Lal,A.D.Shields,B.G.Penn,D.O.Frazier,Solution growth of a novel nonlinear optical material：L-histidine tetrafluoroborate[J]，J.Crystal Growth 1999，204：179-182

[35]K.Selvaraju,R.Valluvan,S.Kumararaman,New nonlinear opticalmaterial：Glycine Hydrofluoride[J]，Materials Letters 2006，60：2848-2850

[36]M.Kato,M.Kiguchi,N.Sugita,Y.Taniguchi,Second-OrderNonlinearity of Mixtures Including p-Nitroaniline Derivatives[J]，J.Phys.Chem.B 1997，101：8856-8859

[37]H.Koshima,H.Miyamoto,I.Yagi,K.Uosaki,Preparation ofCocrystals of 2-Amino-3-nitropyridine with Benzenesulfonic Acids for Second-Order Nonlinear Optical Materials[J]，Crystal Growth＆Design 2004，4：807-811

[38]G.R.Kumara,S.G.Raja,R.Mohana,R.Jayavel,Growth andcharacterization of new nonlinear optical L-threonium acetate single crystals[J]，Journal of Crystal Growth 2005，283：193-197

[39]S.Natarajan,S.A.Martin Britto,E.Ramachandran,Growth，Thermal,Spectroscopic,and Optical Studies of L-Alaninium Maleate,a New Organic Nonlinear Optical Material[J]，Crystal Growth＆Design 2006，6：137-140

[40]M.Arivanandhan,C.Sanjeeviraja,K.Sankaranarayanan,S.K.Das，G.K.Samanta,P.K.Datta Growth of urea doped benzophenone single crystal for nonlinear optical applications[J]，Optical Materials 2006，28：324-330

[41]J.Ramajothi,S.Dhanuskodi,Crystal growth,thermal and opticalstudies on phase matchable new organic NLO material for blue-green laser generation[J]，Journal of Crystal Growth，2006，289：217-223

[42]K.Sethuramana,R.RameshBabua,b，N.Vijayanc,R.Gopalakrishnana，P.Ramasamy,Synthesis,growth of organic nonlinear optical crystal：Semicarbazone of 2-amino-5-chloro-benzophenone and its characterization[J]，Journal of Crystal Growth 2006，290：539-543

[43]R.Valluvan,K.Selvaraju,S.Kumararaman,Growth and characterizationof sulphamic acid single crystals：A nonlinear optical material[J]，Materials Chemistry and Physics 2006，97：81-84

[44]L.Zhu,J.Zhang,D.Chen,X.Feng,Y.Hu,L.Xu,W.Wang,Y.Cui Characteristics of an organic nonlinear optical material urea L-malic acid film[J]，Materials Letters，2006，60：1740-1743

[45]H.J.Ravindra,M.R.Suresh Kumar,Chitharanjan Rai,S.M.Dharmaprakash,A phase-matchable nonlinear optical material N-（3-nitrophenyl）phthalimide：Synthesis,crystal growth and characterization[J]，Journal of Crystal Growth 2006，294：318-322

[46]V.Krishnakumar,S.Manohar,R.Nagalakshmi,Crystal growth andcharacterization of N-hydroxyphthalimide（C8H5NO3）crystal[J]，Spectrochimica Acta Part A 2008，71：110-115

[47]K.Kirubavathi,K.Selvaraju,N.Vijayan,S.Kumararaman，Synthesis,growth and characterization of l-Valinium Picrate a new nonlinear optical crystal[J]，Spectrochimica Acta Part A 2008，71：288-291

[48]M.L.Caroline,S.Vasudevan,Growth and characterization of L-phenylalanine nitric acid,a new organic nonlinear optical material[J]，Materials Letters 2009，63：41-44

[49]W.T.A.Harrison,M.R.Kumar,S.M.Dharmaprakash,H.J.Ravindra，Synthesis,crystal growth,characterizationandstructure-NLO property relationship in 1，3-bis（4-methoxyphenyl）prop-2-en-1-one singlecrystal[J]，Journal of Crystal Growth 2009，311：310-315

[50]S.Natarajan,S.A.Britto,E.Ramachandran,Growth,Thermal，Spectroscopic,and Optical Studies of L-Alaninium Maleate,a New Organic Nonlinear Optical Material[J]，Cryst.Growth＆Design 2006，6：137-140

[51]J.Zyss,I.Ledoux,S.Volkov,V.Chernyak,S.Mukamel,G.P.Bartholomew,G.C.Bazan,Through-Space Charge Transfer and Nonlinear Optical Properties of Substituted Paracyclophane[J]，J.Am.Chem.Soc.2000，122：11956-11962

[52]J.Abe,Y.S.Nemoto,Y.Nagase,Theoretical Study of Hyperpo-larizabilities of Spirolinked Push-Pull Polyenes[J]，J.Phys.Chem.A 1997，101：1-4

[53]J.D.Luo,J.L.Hua,J.G.Qin,J.Q.Cheng,Y.C.Shen,Z，H.Lu,P.Wang,C.Ye,The design of second-order nonlinear optical chromophores exhibiting blue-shifted absorption and large nonlinearities：the role of the combined conjugation bridge[J]，Chem.Commun.2001：171-172

[54]T.Zhang,Y.Zhao,I，Asselberghs,A.Persoons,K.Clays,M.J.Therien,Design,Synthesis,Linear,and Nonlinear Optical Properties of Conjugated（Porphinato）zinc（II）-Based Donor-Acceptor Chromophores Featuring Nitrothiophenyl and Nitroolig-othiophenyl Electron-Accepting Moieties[J]，J.Am.Chem.Soc.2005，127：9710-9720

[55]P.C.Ray,P.Bonifassi,J.Leszczynski,Influence of the CentralMetal Ion on Nonlinear Optical and Two-Photon Absorption Properties of Push-Pull Transition Metal Porphyrins[J]，J.Phys.Chem.A 2008，112：2870-2879

[56]J.Garín,J.Orduna,J.I.Rupérez,R.Alcalá，B.Villacampa,C.Sánchez,N.Martín,J.L.Segura,M.González,Second-order nonlinear optical properties of tetrathiafulvalene-π-（thio）barbituric acid chromophores[J]，Tetrahedron Iett.1998，39：3577-3580

[57]M.González,N.Martín,J.L.Segura,C.Seoane,J.Garín,J.Orduna，R.Alcalá，C.Sánchez,B.Villacampa,Second-order nonlinear optical properties of tetrathiafulvalene-π-3-（dicyanomethylidene）indan-1-one chromophores[J]，Tetrahedron Lett.1999，40：8599-8602

[58]H.Kang,A.Facchetti,H.Jiang,E.Cariati,S.Righetto,R.Ugo,C.Zuccaccia,A.Macchioni,C.L.Stern,Z.Liu,Ultralarge Hyperpolarizability Twistedπ-Electron System Electro-Optic Chromophores：Synthesis,Solid-State and Solution-Phase Structural Characteristics,Electronic Structures,Linear and Nonlinear Optical Properties,and Computational Studies[J]，J.Am.Chem.Soc.2007，129：3267-3286

[59]C.R.Moylan,S.Ermer,S.M.Lovejoy,I.H.Mc Comb,D.S.Leung，R.Wortmann,P.Krdmer,R.J.Twieg，（Dicyanomethylene）pyran Derivatives with C2v Symmetry：An Unusual Class of Nonlinear Optical Chromophores[J]，J.Am.Chem.Soc.1996，118：12950-12955

[60]M.Matsui,M.Tsuge,K.Funabiki,K.Shibata,H.Muramatsu,K.Hirota,M.Hosoda,K.Tai,Hisayoshi Shiozakic,Misa Kimd,Kazumi Nakatsu,Synthesis of azo chromophores containing a perfluorocyclo-alkenyl moiety and their second-order optical nonlinearity[J]，Journal of Fluorine Chemistry 1999，97：207-212

[61]P.Wang,P.Zhu,W.Wu,H.Kang,C.Ye,Design of novelnonlinear optical chromophores with multiple substitutions[J]，Phys.Chem.Chem.Phys.1999，1：3519-3525

[62]B.Cho,S.Lee,S.Lee,K.Son,Y.Kim,J.Doo,G.Lee,T.Kang,Y.Lee,M.Cho,S.Jeon,Octupolar Crystals for Nonlinear optics：1，3，5-Trinitro-2，4，6-tris（styryl）benzene Derivatives[J]，Chem.Mater.2001，13（5）：1438-1440

[63]叶成，方世璧.有机非线性光学[J].化学通报，1990，6：5-12

[64]G.Rojo,G.Martin,F.Agulló-López,G.A.Carriedo,F.J.GarcíaAlonso,J.I.Fidalgo Martinez,Second-Harmonic Response and Relaxation Behavior of High Glass-Transition Temperature Polyphosphazene[J]，Chem.Mater.2000，12：3603-3610

[65]S.R.Marder,J.W.Perry,Nonlinear Optical Polymers：Discoveryto Market in 10 Years[J]，Science 1994，263：1706-1707

[66]H.Saadeh,L.Wang,L.Yu,Supramolecular Solid-State AssembliesExhibiting Electrooptic Effects[J]，J.Am.Chem.Soc.2000，122：546-547

[67]李富友.光响应多功能材料的分子设计、合成、构效关系及其LB膜性质的研究.北京师范大学博士学位论文，2000

[68]C.H.Huang,K.Z.Wang,G.X.Xu,X.S.Zhao,X.M.Xie,Y.Xu，Y.Q.Liu,L.Xu,T.Li,Langmuir Film-Forming and Second Harmonic Generation Properties of Lanthanide Complexes[J]，J.Phys.Chem.1995，99：14397-14402

[69]K.Wostyn,K.Binnemans,K.Claysand,A.Persoons,MolecularFirst Hyperpolarizability Data for Lanthanate Complexes Containing the Hemicyanine Chromophore[J]，J.Phys.Chem.B 2001，105：5169-5173

[70]F.Chaumel,H Jiang,A.Kakkar,Sol-Gel Materials for Second-Order Nonlinear Optics[J]，Chem.Mater.2001，13：3389-3395[71]G.H.Hsiue,R.H.Lee,R.J.Jeng,A New Class of Organic-Inorganic Sol-Gel Materials for Second-Order Nonlinear Optics[J]，Chem.Mater.1997，9：883-888

[72]Z.Yang,C.Xu,B.Wu,L.R.Dalton,S.Kalluri,W.H.Steier,Y.Shi,J.H.Bechtel,Anchoring Both Ends of Chromophores into Sol-Gel Networks for Large and Stable Second-Order Optical Nonlinearities[J]，Chem.Mater.1994，6：1899-1901

[73]G.H.Hsiue,R.H.Lee,R.J.Jeng,Thermally Stable Organic-Inorganic Sol-Gel Materials for Second-Order Nonlinear Optics[J]，Macromol.Symp.2000，156：163-170

[74]O.R.Evans,R.-G.Xiong,Z.Y.Wang,G.K.Wong,W.Lin,CrystalEngineering of Acentric Diamondoid Metal-Organic Coordination Networks[J]，Angew.Chem.，Int.Ed.1999，38：536-538

[75]H.Hou,X.Meng,Y.Song,Y.Fan,Y.Zhu,H.Lu,C.Du,W.Shao，Two-Dimensional Rhombohedral Grid Coordination Polymers[M（bbbt）2（NCS）2]n（M=Co,Mn,or Cd；bbbt=1，1’-（1，4-butanediyl）bis-1H-benzotriazole）：Synthesis,Crystal Structures,and Third-Order Nonlinear Optical Properties[J]，Inorg.Chem.2002，41：4068-4075

[76]H.Hou,Y.Wei,Y.Song,Y.Zhu,L.Li,Y.Fan,Two novel two-dimensional double-sheet layered manganese（II）coordination polymers：synthesis,crystal structures and third-order nonlinear optical properties[J]，J.Mater.Chem.2002，12：838-843

[77]H.Hou,Y.Song,Y.Fan,L.Zhang,C.Du,Y.Zhu,A novelcoordination polymer[Co（NCS）2（bpms）2]n（bpms=1，2-bis（4-pyridylmethyl）disulfenyl）：synthesis,crystal structure and third-order nonlinear optical properties[J]，Inorg.Chim.Acta 2001，316：140-144

[78]H.Hou,Y.Wei,Y.Fan,C.Du,Y.Zhu,Y.Song,Y.Niu,X.Xin，Third-order nonlinear optical properties of three Mn（II）-4，4’-bpy coordination polymers and crystal structure of three-dimensional network[Mn（SO4）（4，4’-bpy）（H2O）2]n[J]，Inorg.Chim.Acta 2001，319：212-218

[79]Frazier C.C,Harvey M.A,Cockerham M.P.etal.Second-harmonicGeneration in Transition-metal-organic Compounds[J]，J.Phys.Chem.1986，90：5703-5706

[80]Qin J,Dai C,Liu D,Influence of the Molecule Configuration on theNonlinear Optical Properties of Organometallic and Coordination Compounds.Preprints of the 2nd China-Japan Bilateral Symp.On Electrophotonic Intelligent Material and Molecular Electronics,Nov.11-13，1994[C].Beijing：94

[81]王兴强.双金属硫氰酸盐配合物晶体的生长和性质研究.山东大学博士学位论文，2002

[82]Ginson P.Joseph,J.Philip,K.Rajarajan,S.A.Rajasekar,A.Joseph A.Pragasam,K.Tamilasaran,S.M.Ravi Kumar,P.Sagayaraj,Growth and characterization of an organometallic nonlinear optical crystal of manganese mercury thiocyanate（MMTC）[J]，Journal of Crystal Growth 2006，296：51-57

[83]X.Q.Wang,D.Xu,M.K.Lu,D.R.Yuan,S.X.Xu,S.Y.Guo,G.H.Zhang,and J.R.Liu,Crystal growth and characterization of a novel organometallic nonlinear-optical crystal：MnHg（SCN）4（C2H6OS）2[J]，Journal of Crystal Growth 2001，224：284-293

[84]Ginson P.Joseph,K.Rajarajan,M.Vimalan,Preema C.Thomas,S.M.Ravi Kumar,M.Gulam Mohamed,G.Mani and P.Sagayaraj,Growth and characterization of semi organic nonlinear optical LHPCL crystals[J]，Cryst.Res.Technol.2007，42：180-185

[85]Alain Mosset,Muriel Bagieu-Beucher,Amelie Lecchi,Rene Masse，Julien Zaccaro,Crystal engineering strategy of thiocyanates for quadratic nonlinear optics.Hg3CdCl2（SCN）6 and Hg4CdBr4（SCN）6[J]，Solid State Sciences 2002，4：827-834

[86]S.M.R.Kumar,N.Melikechi,S.Selvakumar,P.Sagayaraj,Growthand characterization of nonlinear optical bimetallic thiocynate complex of MCCTC crystal[J]，Journal of Crystal Growth 2009，in press

[87]N.Melikechi,JacobPhilip,J.Madhavan,P.Sagayaraj,G.P.Joseph，Studies on the electrical,linear and nonlinear optical properties of Manganese mercury thiocyanate bis-dimethyl sulfoxide,an efficient NLO crystal[J]，Physica B 2009，404：295-299

[88]S.Selvakumar,S.A.Rajasekar,K.Thamizharasan,S.Sivanesan,A.Ramanand,P.Sagayaraj,Thermal,dielectric and photoconductivity studies on pure,Mg +2and Zn +2doped BTCC single crystals[J]，Materials Chemistry and Physics，2005，93：356-360

[89]V.Kannan,N.P.Rajesh,R.Bairava Ganesh,P.Ramasamy,Growthand characterization of Bisthiourea-zinc Acetate,a new nonlinear optical material[J]，Journal of Crystal Growth 2004，269：565-569

[90]S.Selvakumar,S.M.Ravi Kumar,Ginson P.Joseph,K.Rajarajan，J.Madhavan,S.A.Rajasekar,P.Sagayaraj,Growth and characterization of pure and doped bis（thiourea）cadmium acetate single crystals[J]，Materials Chemistry and Physics，2007，103：153-157

[91]Y.Yan,Q.Fang,W.Yu,D.Yuan,Y.Tian,M.Jiang,I.D.WilliamsZ.Cai,Synthesis,structure and non-linear optical properties of FeHg（SCN）4 and MnHg（SCN）4[J]，Acta Chim.Sinica 1999，57：1257-1261

[92]X.Wang,D.Xu,M.Lu,D.Yuan,G.Zhang,S.Xu,S.Guo,X.Jiang,J.Liu,C.Song,Quan Ren,J.Huang,Y.Tian,Growth and properties of UV nonlinear optical crystal ZnCd（SCN）4[J]，Materials Research Bulletin 2001，36：1287-1299

[93]X.Q.Wang,D.Xu,D.R.Yuan,Y.P.Tian,W.T.Yu,S.Y.Sun,Z.H.Yang,Q.Fang,M.K.Lu,Y.X.Yan,F.Q.Meng,S.Y.Guo,G.H.Zhang,M.H.Jiang,Synthesis,structure and properties of a new nonlinear optical material：zinc cadmium tetrathiocyanate[J]，Materials Research Bulletin 1999，34：2003-2011

[94]H.O.Marcy,M.J.Rosker,L.F.Warren,P.H.Cunningham,C.A.Thomas,L.A.Deloach,S.P.Velsko,C.A.Ebbers,J.H.Liao,L-Histidine tetrafluoroborate：a solution-grown semiorganic crystal for nonlinear frequency conversion[J]，Opt.Lett.1995，20：252-254

[95]Y.Tian,C.Duan,C.Zhao,X.You,T.C.W.Mak,Z.Zhang，Synthesis,Crystal Structure,and Second-Order Optical Nonlinearity of Bis（2-chlorobenzaldehyde thiosemicarbazone）cadmium Halides（CdL2X2；X=Br,I）[J]，Inorg.Chem.1997，36（6）：1247-1252

[96]R.Sankar,C.M.Raghavan,R.Jayave,Bulk Growth andCharacterization of Semi-Organic Nonlinear,Optical Bis Thiourea Bismuth Chloride Single Crystals[J]，Cryst.Growth＆Design 2007，7：501-505

[97]M.Jiang Q.Fang,Organic and Semiorganic Nonlinear OpticalMaterials[J]，Adv.Mater.1999，11：1148-1153

[98]K.Kirubavathi,K.Selvaraju,S.Kumararaman,Growthandcharacterizationof a new metal-organic nonlinear optical bis（thiourea）cadmium zinc chloride single crystals[J]，Spectrochimica Acta Part A 2008，71：1-4

[99]G.S.Murugan,P.Ramasamy,Growth and characterization of metal-organic crystal：Tetrathiourea cobalt chloride（TTCoC）[J]，Journal of Crystal Growth 2009，311：585-588

[100]P.Ren,T.Liu,J.Qin,C.Chen,A new approach to suppressnonlinearity-transparency trade-off through coordination chemistry：syntheses and spectroscopic study on second-order nonlinear optical properties of a series of square-pyramidal zinc（II）complexes[J]，Spectrochimica Acta Part A 2003，59：1095-1101

[101]H.Zhang,D.E.Zelmon,G.E.Price,B.K.Teo,Wide SpectralRange Nonlinear Optical Crystals of One-Dimensional Coordination Solids[Et4N][Cd（SCN）3]and[Et4N][Cd（SeCN）3]and the General Design Criteria for[R4N][Cd（XCN）3]（Where R=Alkyl and X=S,Se,Te）as NLO Crystals[J]，Inorg.Chem.2000，39：1868-1873

[102]H.Zhang,X.Wang,K.Zhang,B.K.Teo,Molecular and crystalengineering of a new class of inorganic cadmium-thiocyanate polymers with host-guest complexes as organic spacers,controllers,and templates[J]，Coordination Chemistry Reviews 1999，183：157-195

[103]O.R.Evans,W.Lin,Crystal Engineering of NLO Materials Basedon Metal-Organic Coordination Networks[J]，Acc.Chem.Res.2002，35（7）：511-522

[104]R.Xiong,J.Zuo,X.You,Z.Bai,B.F.Abrahams,C.Che H.Fun，Opto-electronic multifunctional chiral diamondoid-network coordination polymer：bis{4-[2-（4-pyridyl）ethenyl]benzoato}zinc with high thermal stability[J]，Chem.Commun.2000：2061-2062

[105]Z.Chen,R.Xiong,B.F.Abrahams,X.You.C.Che,An unprecedentedsix-fold anion-type chiral diamondoid-like eight-coordinate Cd（II）coordination polymer with a second-order nonlinear optical effect[J]，J.Chem.Soc.，Dalton Trans.2001：2453-2455

[106]R.Prajapati,L.Mishra,K.Kimura,P.Raghavaiah,Metal-organicframeworks（MOFs）constructed from Zn II/Cd II-2，2’-bipyridines and polycarboxylic acids：Synthesis,characterization and microstructural studies[J]，Polyhedron 2009，28：600-608

[107]W.Sun,C.Tian,Q.Yue,E.Gao,Synthesis and crystal structure ofcadmium（II）coordination polymers with 3-and 4-pyridylacrylic acids[J]，Journal of Molecular Structure 2009，920：189-195

[108]W.F.Guo,X.B.Sun,J.Sun,X.Q.Wang,G.H.Zhang,Q.Ren，D.Xu,Nonlinear optical absorption of a metal dithiolene complex irradiated by different laser pulses at near-infrared wavelengths[J]，Chemical Physics Letters 2007，435：65-68

[109]C.S.Liu,X.S.Shi,J.R.Li,J.J.Wang,X.H.Bu,Cd（II）Coordination Architectures with Mixed Ligands of 3-（2-Pyridyl）pyrazole and Pendant Carboxylate Ligands Bearing Different Aromatic Skeletons：Syntheses,Crystal Structures,and Emission Properties[J]，Cryst.Growth Des.2006，6：656-663

[110]W.B.Lin,O.R.Evans,R.G.Xiong,Z.Y.Wang,SupramolecularEngineering of Chiral and Acentric 2D Networks.Synthesis,Structures,and Second-Order Nonlinear Optical Properties of Bis（nicotinato）zinc and Bis{3-[2-（4-pyridyl）ethenyl]benzoato}cadmium[J]，J.Am.Chem.Soc.1998，120：13272-13273

[111]K.C.Mondal,O.Sengupta,M.Nethaji,P.S.Mukherjee，Assembling metals（Co II and Mn II）with pyridylcarboxylates in the presence of azide：synthesis,structural aspects and magnetic behavior of three coordination polymers[J]，Dalton Trans.2008：767-775.

[112]A.Hilton,T.Renouard,O.Maury,H.LeBozec,I.Ledoux,J.Zyss，New bipyridyl ligands bearing azo-and imino-linked chromophores.Synthesis and nonlinear optical studies of related dipolar zinc complexes[J]，Chem.Commun.1999：2521-2522

[113]K.Sénéchal,O.Maury,H.L.Bozec,I.Ledoux,J.Zyss,Zinc（II）asa Versatile Template for the Design of Dipolar and Octupolar NLO-phores[J]，J.Am.Chem.Soc.2002，124：4560-4561

[114]A.Kandasamy,R.Siddeswaran,P.Murugakoothan,P.S.Kumar，R.Mohan,Synthesis,Growth,and Characterization of L-Proline Cadmium Chloride Monohydrate（L-PCCM）Crystals：A New Nonlinear Optical Material[J]，Cryst.Growth＆Design 2007，7：183-186

[115]V.S.Shankar,R.Siddheswaran,R.Sankar,R.Jayavel,P.Murugakoothan,Synthesis and growth of sodium bitartrate monohydrate a new organometallic nonlinear optical single crystal[J]，Current Applied Physics 2009 in press

[116]M.L.Caroline,A.Kandasamy,R.Mohan,S.Vasudevan,Growthand characterization of dichlorobis L-proline Zn（II）：A semiorganic nonlinear optical single crystal[J]，Journal of Crystal Growth 2009，311：1161-1165

[117]V.S.Shankar,R.Siddheswaran,R.Sankar,R.Jayavel,P.Murugakoothan,Growth and characterization of new semiorganic nonlinear optical single crystal L-Phenylalanine L-Phenylalaninium perchlorate（LPPAPC）[J]，Materials Letters 2009，63：363-365

[118]G.A.Babu,P.Ramasamy,Synthesis,crystal growth andcharacterization of novel semiorganic nonlinear optical crystal：Dichlorobis（l-proline）zinc（II）[J]，Materials Chemistry andPhysics 2009，113：727-733

[119]P.C.Ittyachan,D.P.Thomas,M.Anand,P.Palanichamy，Sagayaraj,Materials Growth and characterization of semiorganic non-linear optical LHB single crystal[J]，Chemistry and Physics 2005，93：272-276

[120]W.S.Wang,M.D.Aggarwal,J.Choi,T.Gebre,A.D.Shields,B.G.Penn,D.O.Frazier,Solvent effects and polymorphic transformation of organic nonlinear optical crystal L-pyroglutamic acid in solution growth processes：I.Solvent effects and growth morphology[J]，J.Cryst.Growth 1999，198：578-582

[121]Y.Wang,H.Fan,H.Wang,X.Chen,Homochiral helical wavelike（4，4）networks constructed by divalent metal ions and S-carboxymethyl-L-cysteine[J]，Journal of Molecular Structure 2005，740：61-67

[122]J.Qin,C.Dai,D.Liu,C.Dai,C.Chen,B.Wu,C.Yang,C.Zhan,Influence of the molecular configuration on second-order nonlinear optical properties of coordination compounds[J]，Coord.Chem.Rev.1999，188：23-34