【作者】 张莹；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2009， 博士

【摘要】 酞菁及其类似物因为其在光学记录、非线性光学应用、光吸收、电子传导、光电导、能量转化、电极、化学传感器和催化等多方面的功能,吸引了广泛的关注。柱形盘状的中间相液晶分子在半导和光导装置,发光二极管和传感器方面有极大的应用潜力。酞（萘）菁,作为盘状芳香环,能容易的被各种各样的长链烷硫基、烷氧基和甲氧基取代,可以从晶体材料转变成液晶材料。侧链取代的酞菁衍生物通常形成一个超分子体,显示出其柱状液晶相性质,为结合酞菁的光电性质和传统的液晶体系的定向控制提供可能。另外,光致变色化合物由于其在光能记忆、信息存储、涂料、颜料以及相关工业中的潜在应用价值而越来越受到重视。近年来,设计和合成具有全新结构或有利于实际应用的这类物质己成为一个很热门的领域。我们的研究工作主要集中在以下几个方面:1、三明治型二层[3,4,12,13,21,22,30,31-八（十二烷硫基）取代]-2,3-萘菁稀土配合物的合成、谱学表征和液晶性质研究一系列三明治型二层[3,4,12,13,21,22,30,31-八（十二烷硫基）取代]-2,3-萘菁稀土配合物M[Nc(SC₁₂H₂₅)₈]₂（M=Nd,Eu,Gd,Tb,Y,Ho,Er）（1-7）是通过6,7-二（十二烷硫基）-2,3-二氰基萘与稀土的乙酰丙酮盐M（acac）₃·nH₂O在DBU的催化下在正辛醇中以回流温度四聚而成。这一系列三明治型双层配合物通过元素分析,各种光谱如紫外可见光谱,近红外,红外以及质谱进行了表征。他们的液晶性质通过偏光显微镜（POM）、示差扫描量热（DSC）和X射线衍射法（XRD）进行了研究。这些烷硫基取代的双层稀土萘菁配合物在很宽的温度区间42-243℃内,可以形成稳定的六角柱状相液晶态。液晶相的温度区间与配合物中心金属离子半径有关。并且,这些化合物由X射线衍射而测得的分子堆积也受中心金属离子半径的影响。2、三明治型三层[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]-酞菁稀土配合物的合成、谱学表征和液晶性质研究一系列三层[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]-酞菁稀土配合物M₂[Pc(OC₈H₁₇)₈]₃[M=Eu,Gd,Y,Lu]（1-4）通过双层[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]-酞菁稀土配合物M[Pc(OC₈H₁₇)₈]₂与稀土的乙酰丙酮盐M（acac）₃·nH₂O在1,2,4-三氯苯中回流生成。这些化合物通过元素分析,各种光谱如紫外可见光谱,近红外,红外、质谱以及核磁进行了表征。他们的液晶性质通过偏光显微镜（POM）、示差扫描量热（DSC）和X射线衍射法（XRD）进行了研究。这些烷氧链取代的化合物在很宽的温度区间83-305℃内的液晶相为矩形柱状相。伴随着镧系收缩,液晶相的转变温度和温度区间都随之降低和变小。而且,X射线衍射而测得的分子的堆积也受中心金属离子半径的影响。3、三明治型[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]-酞菁类金属钆配合物的液晶性质研究一系列六个[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]的包含对称和不对称的双层和三层的酞菁钆的配合物Gd（Pc）[Pc(OC₈H₁₇)₈]（1）,Gd[Pc(OC₈H₁₇)₈]₂[Pc(OC₈H₁₇)₈=2,3,9,10,16,17,23,24-八（辛烷氧基）取代酞菁]（2）,（Pc）Gd（Pc）Gd[Pc(OC₈H₁₇)₈]（3）,（Pc）Gd[Pc(OC₈H₁₇)₈]Gd（Pc）（4）,（Pc）Gd[Pc(OC₈H₁₇)₈]Gd[Pc(OC₈H₁₇)₈]（5）和Gd₂[Pc(OC₈H₁₇)₈]₃（6）的液晶相变行为通过偏光显微镜（POM）、示差扫描量热（DSC）和X射线衍射法（XRD）进行了研究。他们的熔化温度与三明治的分子结构有关,随着分子层数的增加和烷氧链取代的酞菁在分子中所占比例的增大而提高。液晶相显示的六角柱状相或矩形柱状相也与分子结构有关,表明了在液晶相的形成过程中,烷氧链的影响和π-π堆积所起的重要作用。另外,这些双层和三层的酞菁钆的配合物形成的液晶相在经过热处理和退火后在室温下显示出超强的稳定性,这也非常有利于其在分子电子器件方面的应用。4、三明治型双层[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]酞菁铕配合物的液晶性质在OFET中的应用一个三明治型双层[2,3,9,10,16,17,23,24-八（辛烷氧基）取代]酞菁铕配合物Eu[Pc(OC₈H₁₇)₈]₂被设计合成并用偏光显微镜（POM）、示差扫描量热（DSC）和X射线衍射法（XRD）的方法研究了它们的液晶性质,包括相变温度,液晶相织构类型,分子堆积状况。化合物在其两个液晶区间69-93℃和93-196℃内分别呈现出矩形柱状相Col_r和六角柱状相Col_h。利用其液晶性质,用真空镀膜机甩膜在经过六甲基硅烷（HMDS）处理的SiO₂/Si基片上,应用热处理的方法制备了有机场效应晶体管并研究了它的场效应。通过测量膜在Col_r的分子堆积模式下的场效应晶体管的工作Ⅰ-Ⅴ曲线,得到了0.07 cm² V^-1 s^-1的迁移率和5.4×10²的开关比。5、新型二噻吩乙烯基四氮杂卟啉与酞菁混杂不对称双层稀土铕配合物的合成、表征及光致变色性质研究一个新型具有光致变色性质的三明治型二噻吩乙烯基四氮杂卟啉和[2,3,9,10,16,17,23,24-八（癸烷氧基）取代]酞菁混杂的不对称三明治型双层稀土铕配合物EuH（Pz’）（Pc’）[Pz’=Pz（C₇H₉S）₈,Pc’=Pc(OC₁₀H₂₁)₈]是通过Eu（acac）₃·nH₂O、自由酞菁H₂Pc(OC₁₀H₂₂)₈和具有光致变色性质的配体1,2-二氰基-1,2-二（2’,4’,5’-三甲基-3-噻吩）乙烯用“一步法”合成出来。配合物通过元素分析、质谱、紫外可见光谱、红外以及核磁进行了表征。电化学性质通过循环伏安法（CV）和差分脉冲伏安法（DPV）进行了研究,显示出三个准可逆单电子氧化过程和四个准可逆单电子还原过程,表明对于高密度存储来说这是一个电活性较高的化合物。其光致变色行为通过电子吸收光谱进行了研究,表明了作为非破坏性读出信息材料,具有巨大潜力。更多还原

【Abstract】 Phthalocyanines and their analogues have attracted considerable attention as versatile materials for optical recording media,nonlinear optical application,light absorption,electric conduction,photoconduction,energy conversion,electrode, chemical sensor,and catalyst.Columnar discotic mesophase liquid crystals have shown great potential application in semiconducting and photoconducting devices, light-emitting diodes and sensors due to their anisotropic charge carrier transport properties.（Na）phthalocyanines,as disc-shaped aromatic rings,can be facilely modified upon addition of various kinds of long alkyl,alkoxy and alkyloxymethyl side chains,therefore,to transform the crystalline materials to the liquid crystalline materials.Phthalocyanine derivatives substituted with appropriative side chains generally form a supramolecular organization and demonstrate columnar mesophases, which afford the possibility of combining the opto-electronic properties of phthalocyanines（Pcs） with the orientation control of conventional liquid-crystal systems.Moreover,photochromic materials are attached much importance to owing to their potential application in the areas of optical memory,information storage, dopes,pigments and other correlative industries.In recent years,it has become a popular field to design and synthesize this kind of materials with novel structures or availing in practice.Our research work in these fields has been focused on the following respects:1.Synthesis and Liquid Crystal Behavior of Bis[3,4,12,13,21,22,30,31-oeta（dodecylthio）-2,3-naphthalocyaninato]Rare Earth Complexes A series of novel bis[3,4,12,13,21,22,30,31-octa（dodecylthio）-2,3-naphthalocyaninato]rare earth（Ⅲ） complexes M[Nc(SC₁₂H₂₅)₈]₂[M=Nd,Eu, Gd,Tb,Y,Ho,Er]（1-7） have been prepared by tetramerization of 2,3-bis（dodecylthio）-6,7-dicyanonaphthalene with M（acac）₃·nH₂O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene（DBU） in refluxing n-octanol.These sandwich double-decker complexes were characterized by elemental analysis and various spectroscopic methods including UV-vis,near IR,IR,and mass spectroscopies.Their liquid crystal behavior was studied by polarized optical microscope（POM）, differential scanning calorimeter（DSC）,and X-ray diffraction.These alkylthio-substituted bis（2,3-naphthalocyaninato） rare earth complexes yield a hexagonal columnar liquid crystal whose wide temperature range is between 42 and 243℃.The stable temperature domain of the mesophase shows a trend to be dependent on the central rare earth ionic size.In contrast,the molecular packing of these complexes as revealed by X-ray diffraction was found to be almost independent of the ionic size of the central rare earth.2.Synthesis and Liquid Crystal Behavior of Tris[2,3,9,10,16,17,23,24-octakis（octyloxy）phthalocyaninato]Rare Earth ComplexesA series of tris[2,3,9,10,16,17,23,24-octakis（octyloxy）phthalocyaninato]rare earth（Ⅲ） complexes M₂[Pc(OC₈H₁₇)₈]₃[M=Eu,Gd,Y,Lu]（1-4） has been prepared by the reaction of corresponding bis[2,3,9,10,16,17,23,24-octakis（octyloxy）-phthalocyaninato] rare earth complexes with M（acac）₃·nH₂O in refluxing 1,2,4-trichlorobenzene（TCB）.These liquid crytalline sandwich triple-decker complexes were characterized by elemental analysis and various spectroscopic methods including ¹H NMR,UV-vis,IR and mass spectroscopies.Their liquid crystal phase transition behavior was studied by Polarized Optical Microscope（POM）, Differential Scanning Calorimeter（DSC） and X-ray diffraction.The complexes,with octyloxy attached as side chains,showed rectangular columnar liquid crystal phases in liquid crystal temperature range between 83 and 305℃.Along with the rare earth contraction,both the transition temperature and the wide temperature range of the mesophase show slight but obvious decrease trend,respectively,in the same order.In contrast,the molecular packing of these complexes as revealed by X-ray diffraction was found to be almost independent of the ionic size of the central rare earth. 3.Liquid Crystal Behavior of 2,3,9,10,16,17,23,24-Octakis（octyloxy）-phthalocyanine -containing Gadolinium Sandwich ComplexesA series of six liquid crystalline phthalocyaninato gadolinium sandwich complexes including two double-deckers Gd（Pc）[Pc(OC₈H₁₇)₈]（1）[Pc(OC₈H₁₇)₈= 2,3,9,10,16,17,23,24-octakis（octyloxy）phthalocyanine]and Gd[Pc(OC₈H₁₇)₈]₂（2） and four triple-deckers（Pc）Gd（Pc）Gd[Pc(OC₈H₁₇)₈]（3）,（Pc）Gd[Pc(OC₈H₁₇)₈]Gd（Pc）（4）, （Pc）Gd[Pc(OC₈H₁₇)₈]Gd[Pc(OC₈H₁₇)₈]（5）,and Gd₂(OC₈H₁₇)₈]₃（6） have been designed and their liquid crystal phase transition behavior was systematically studied by differential scanning calorimeter（DSC）,X-ray diffraction and polarized optical microscope（POM）.The clearing point seems to show a dependence on the molecular structure of sandwich compounds,increasing from double-decker to triple-decker and along with the increase in the number of substituted 2,3,9,10,16,17,23,24-octakis（octyloxy）phthalocyanine ligand both in the double- and triple-decker compounds.The liquid crystalline mesophases displayed hexaganol columnar and/or rectangular columnar molecular arrangement depending on the molecular structure of sandwiches,suggesting the cooperation of theπ-πstacking and the influence of octyloxy side chains on the liquid crystalline formation.In addition, textures of this series of double- and triple-decker sandwich compelxes formed in the liquid crystalline mesophase exhibit high stability even after the mesophases of the compounds were treated with heating into the clear isotropic liquid and cooling to the room temperature,which is expected to be an efficient method for constructing molecular electronic devices.4.OFET Properties of the Liquid Crystal Material Bis[2,3,9,10,16,17,23,24-oetakis（octyloxy）phthalocyaninato]Europium（Ⅲ） Complex.The liquid crystal and OFET properties of the free-radical sandwich complex bis（octakis（octyloxy）phthalocyaninato）europium（Ⅲ）,Eu[Pc(OC₈H₁₇)₈]₂ have been studied.This compound displays multimesomorphic thermotropic behavior with two columnar liquid crystalline phases,Col_r and Col_h,between the freshly precipitated crystalline solid at room temperature,K,and the isotropic liquid,I,at 196℃.The ordered mesophases of the compound is demonstrated by the atomic force microscope （AFM）.With the help of spin-coating technique,the typical liquid crystal double-decker complex has been fabricated into organic field effect transistors（OFET） with bottom contact configuration on hexamethyldisilazane（HMDS）-treated SiO₂/Si substrate.The carrier mobility for hole as high as 0.07 cm² V^-1 s^-1 and current modulation of 5.4×10² have been reached for the devices of the mesophase Col_r of the double-decker compound.5.A Novel Photochromic and Electrochromic Europium Tetraazaporphyrinato and Phthalocyaninato Heteroleptic Double-Decker for Information Storage. General Synthesis,Spectroscopic,and Electrochemical CharacterizationA novel tetraazaporphyrinato and phthalocyaninato mixed heteroleptic double-decker sandwich rare earth compound with photochromic and electrochromic features has been facilely synthesized by one-pot reaction using Eu（acac）₃·nH₂O, metal-free phthalocyanine H₂Pc’（Pc’=2,3,9,10,16,17,23,24-octakis（decyloxy）-phthalocyanine）, and the photochromic precursor 1,2-dicyano-1,2-bis（2,3,5-trimethyl-3-thienyl）ethane as starting materials.The compound was well characterized by elemental analysis,and various spectroscopic methods including UV-vis,IR,1H NMR,and mass spectroscopies.The electrochemical behavior of this compound was studied by cyclic voltammetry（CV） and differential pulse voltammetry（DPV） methods,which showed up to three one-electron oxidation and four one-electron reduction processes,demonstrating an electro-active compound for high density information storage.The photochromic performance of the compound was detected by electronic absorption spectra,suggesting the compound to be good candidate for non-destructive readout by means of UV-vis spectroscopy.更多还原