【作者】 李蕾；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2008， 博士

【摘要】 有机光致变色化合物由于其在光能记忆、信息存贮、涂料、颜料以及相关工业中的潜在应用价值而受到越来越多的重视。近年来,二芳基乙烯特别是二噻吩乙烯（BTE）,因为具有良好的热稳定性和优良的耐疲劳性而成为这类化合物的杰出代表。因此,人们在合成这类化合物方面倾注了许多的热情和精力。一方面是期望构建可能具有先进的或新的特性的新型分子材料,另一方面是为了满足实际应用的需要,对化合物进行修饰,使之可与现有的应用技术手段和条件相匹配。本论文的研究目的在于如何将二噻吩乙烯基团连接到卟啉、酞菁等大环分子上面,这一方面有利于光致变色性能的提升,另一方面也使得基于大环分子π-π作用的分子自组装成为可能。论文的主要内容总结如下:1、二噻吩乙烯基四氮杂卟啉锌配合物的光致变色性质及无损读取性质研究采用“一步法”合成了2,3,7,8,12,13,17,18-八-（2’,4’,5’-三甲基-3′-噻吩）四氮杂卟啉-锌配合物,通过电子吸收光谱及核磁共振（NMR）研究了该配合物的光致变色性质,并利用计算和实验的方法研究了配合物的光致开、关环异构体的红外吸收特性的变化,研究其红外无损读取的可行性。结果表明,配合物在365 nm和700 nm波长的光照射下发生了可逆的光致开关环反应,其中,仅在四氮杂卟啉大环对位位置的两对二噻吩乙烯基团发生了关环。氮杂卟啉大环结构抑制了二噻吩基乙烯的镜面对称结构,从而有效提高了化合物的光致关环量子产率。开环和关环异构体的红外谱图的显著变化及理论化学计算结果表明该二芳基乙烯衍生物光致变色反应后其关环异构体在1705 cm^-1处出现的强吸收峰可以用于红外无损读取。而1441和1489 cm^-1处出现的吸收峰也可用于识别该配合物的光致异构化过程。本章还对化合物的荧光光谱进行了分析,发现它在光致变色前后有明显的变化,探讨了利用其荧光光致变色前后的不同作为非破坏性读出方式的可行性。2、二芳基乙烯和冠醚取代不对称四氮杂卟啉的合成、表征及自组装通过简单的固相反应,制备得到了一系列的四氮杂卟啉（TAP）-铜的配合物,在四氮杂卟啉的周边的四个取代位置,取代着不同数目的二噻吩乙烯（BTE）和15-冠-5（化合物1-5）。通过电子吸收光谱以及元素分析等方法,对所合成的化合物进行了表征。详细研究了四氮杂卟啉环上二噻吩乙烯和15-冠-5的取代后对化合物的电子吸收谱,红外光谱,光致变色性能的影响。考虑到化合物中15-冠-5基团的存在,我们对K⁺存在下产品在溶液中和使用溶液混合法的自组装行为也进行了研究。由于BTE取代基的刚性结构,使得溶液中在K⁺存在下引发的二聚体不能以共面的形式进行连接,从而形成了一维的链状超结构。在溶液混合法中,冠醚配体的数目和分子的开关环状态都会对聚集体的形貌产生影响。3、模板法制备不对称冠醚取代四氮杂卟啉锌配合物空心球通过固相反应,合成了取代了三个二噻吩乙烯基团（BTE）和一个15-冠-5基团、具有平面片状构型的两亲四氮杂卟啉锌ZnA₃B。因为15-冠-5基团的亲水性和二噻吩乙烯基团的亲油性,使得化合物的分子具有双亲性。该化合物被证明可以通过自组装的方式形成具有空心结构的纳米球。使用扫描电镜（SEM）、透射电镜（TEM）、电子散射谱（EDS）、X-射线衍射（XRD）以及电子吸收光谱对空心纳米结构的组成及结构进行了表征。基于已知的实验事实,提出了以K⁺为模板的空心球生成机理。在这些纳米颗粒中,K⁺的加入阻止了其从周边到中心的手性传递,使得整个分子的螺旋性丧失,从而使得其结构得以保持。这种具有可控性的手性材料在光电材料以及传感器等方面有着潜在的应用价值。4、新型二噻吩乙烯基取代的混合四氮杂卟啉酞菁三明治型化合物的合成、表征及性质研究将常规用来制备酞菁类化合物的方法应用到合成四氮杂卟啉化合物上,成功得到了首例不对称混杂四氮杂卟啉、酞菁的三明治型稀土金属配合物Eu₂[TAP（C₇H₉S）₈][Pc（15C5）₄]₂,通过核磁共振氢谱、红外、质谱、元素分析、紫外可见吸收光谱对所合成的化合物进行了必要的表征。在研究中我们发现该化合物具有优良的光致变色性质,是具有全新结构的一类新型的二噻吩乙烯光致变色化合物,可以通过光致变色开/关环反应来调节氮杂卟啉、酞菁的共轭体系的大小,它的合成方法新颖,操作方便,具有一定的实用性。更多还原

【Abstract】 Due to the potential application in optical recording,information storage,pigment, organic photohromic compounds has attract more and more attentions.Among these kinds of photochromic compound,diarylethene,especially bisthienylethene has been the focus of attention because of their outstanding thermal stability and fatigue resistance.These years,a lot of efforts have been devoted to synthesizing these kinds of photochromic compounds,which not only contains the synthesis of new molecule materials with better performace,but also contains the modification of the molecules with the functional group.The main aim of this dissertation is to explore the new and effective method for the synthesis of tetrazaporphyrin or phthalocyaninato with BTE substituent,which will not only improve the photochromic performance of the compounds,but also facilitate the self-assemblies of the molecules based on intra-molecularπ-πinteractions.The main points of thedissertations are summarized as follows:1、Synthesis of TAP-BTE zinc complex with photochromic property and its application in non-destructive readoutA photochromic 1,2-bisthienylethenes（BTEs） substituted tetraazaporphyrinato（TAP） zinc complex, 2,3,7,8,12,13,17,18-octakis（2’,4’,5’-trimethyl-3’-thienyl）tetraazaporphyrizine zinc,was synthesized by "one-pot" reaction,and was characterized by spectroscopic methods as well as the elemental analysis.The changes in the electronic absorption spectrum and ¹H-NMR indicate that this BTE-TAP hybrid underwent reversible photocyclization and cycloreversion by irradiation with 365 and 730 nm light in CHCl₃ solution,respectively. However,the reversible photocyclization only occurs on the BTE group in the opposite position.The macromolecules of tetrazaporphin restricted the symmetrical structure of BTE group,which greatly improved the photochromic performance of the compounds. Comparisons between the experimental and computational IR spectra clarified the significant difference of the open- and closed-ring isomers,which indicate that this diarylethene derivative can be used in non-destructive readout by IR light at 1705 cm^-1. The absorption peak at 1441 and 1489cm-1can also be used in the identification of the photocyclization process.Decrease of the molecule symmetry or increase the molecular dipole moment will change the IR vibration intenstity,which will greatly facilitate the nor-destructive readout process.The photo-luminescence properties of the compounds are also investigated,which clearly shows that the spectrum of the compound greatly changed before and after the photocycliztion process.The possibilities of using the PL spectrum as the non-destructive readout method are also carefully discussed.2.Tetrazaporphyrin substituted with crown ether and diarylethen group:synthesis, characterizations and its self-assembliesA series of novel tetraazaporphyrinato（TAP） copper compounds substituted with different number of 15-crown-5 voids and photochromic 1,2-bisthienylethenes（BTEs） 1-5 were synthesized by "one-pot" reaction,and were characterized by spectroscopic methods as well as the elemental analysis.The effects of BTE and 15-crown-5 substituents number and molecular symmetry on the electronic absorption spectra, infra-red（IR） spectra,photochromic performance are carefully investigated.All the BTE-TAP hybrids have presented photocyclization and cycloreversion with different quantum yield by irradiation with 365 and 700 nm light in CHCI3 solution,respectively. Considering the existence of 15-crown-5 ether group in the molecules,the interfacial self-assemble behavior of the compound are also investigate,which clearly demonstrate that the steric hindrance derived from the BTE（s） substituents embarrasses the cofacial dimerization of the compounds,and only linear dimers formed as a result.The number of 15-crown-5 ether group and the open/close state of the ring will greatly affect the morphologies of the aggregates.3、A template method for the synthesis of crown ether substituted tetrazaporphyrin zinc hollow spheresA plate-like tetraazaporphyrinato（TAP） zinc compounds substituted with different number of 15-crown-5 voids and photochromic 1,2-bisthienylethenes（BTEs） 1-5 were synthesized by "one-pot" reaction.The compound show amphilic property due to the hydrophilic property of 15-crown-5 group and hydrophobic property of BTE group. This compound has been prove to form uniformly-sized multilarnellar hollow nanospheres with a mean diameter of 200 nm under the template construction of potassium ions.Scanning Electron Microscopy（SEM）,transmission electron microscopy（TEM）,Electron Dispersion Spectrum（EDS）,X-ray Diffraction（XRD） and electron absorption spectrum are employed to characterize the structure and component of the hollow spheres.Based on the experimental facts,potassium ion template formation mechanism of the hollow spheres is proposed.In these nanoparticles,the addition of K⁺ restricted the chirality transfer from the peripheral,which finally lead to the loss of helicity of the compound.This kind of controllable chiral material will have potential application in optical electric materials and sensors.4、Novel sandwiched complex with BTE substituted tetrazaporphyrin and phthalocyanines:synthesis,characterizations and its properties.A conventional route which is usually used in the synthesis of phthalocyaninato are employed in the synthesis of tetrazaporphyrin derivatives,which finally lead to the first sandwiched rare earth complex Eu₂[TAP（C₇H₉S）₈][Pc（15C5）₄]₂.The ¹H-NMR,IR, Mass,elemental analysis and electron absorption spectrum are employed to characterize the compound.Our study shows that this compound show excellent photochromic performance.It can tune the scope of conjugation by the ring open or ring close reaction, which is applicable due to is novelty and facility.更多还原