【作者】 路桂芬；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2009， 博士

【摘要】 卟啉酞菁化合物以及三明治型稀土卟啉酞菁配合物作为新型的功能材料,由于其具有迷人的、独特的光学、电学、磁性以及其它的与其分子内部大环之间π-π相互作用有关的物理性质,因此使得它们在分子电子学、分子信息存储和非线性光学上具有潜在的应用价值,在材料科学领域拥有广阔的应用前景。近年来,该类配合物的有序超分子聚集体和纳米尺度组装研究已经成为了热点领域。但是,对化学家和材料学家来说,通过模拟和设计分子的结构调节分子间作用力以获得所希望得到有机纳米结构材料的形貌仍然是一个挑战。本论文主要设计、合成了具有特定分子结构和特殊性质的新型卟啉和酞菁大环配合物;通过自组装方法,将上述合成的目标化合物组装成各种高级有序的聚集体材料,探讨组装过程的机理和动力学过程,研究分子结构对分子在聚集体中排列方式的影响以及聚集体结构和性质之间的关系,总结变化规律,系统的研究总结各种具有更高性能的新型分子功能材料的思路和方法。其内容主要包括以下几个部分:1、两亲性卟啉配合物自组装纳米结构的研究有机功能分子自组装得到的有序纳米结构被预期在纳米科学与纳米技术中获得广泛的应用。自组装过程是一种自发的过程,是指分子间通过非共价键例如,氢键、配位键、堆积效应、静电相互作用、亲/疏水相互作用等形成的结构稳定、复杂有序且具有某种特定功能的纳米聚集体或超分子结构的过程。近十年来,通过分子的相互作用进行有机分子纳米结构自组装的研究一直是广大科研工作者研究的热点。各种各样形貌的有机纳米结构的报道层出不穷:纳米线、纳米棒、纳米颗粒和纳米管等等。然而,对化学家和材料学家来说,通过模拟和设计分子的结构调节分子间作用力以获得所希望的有机纳米结构材料的形貌仍然是一个挑战。在本章中,我们设计了三种卟啉分子Metal free tetrakis（4-hydroxyphenyl）porphyrin H₂THPP（1）,Tetrakis（4-hydroxyphenyl）porphyrinato copper complex CuTHPP（2）,和Metal freetetraphenylporphyrin H₂TPP（3）。利用相转移方法,把它们组装成有机纳米聚集体。参考化合物3利用紫外（UV）、红外（FT-IR）、透射电镜（TEM）、扫描电镜（SEM）、原子力显微镜（AFM）等表征手段系统研究了典型两亲性化合物1和2在水溶液中的自组装性质。对比研究表明,在自组装过程中,除了π-π堆积作用外,氢键和金属配位键的竞争和协同作用使得分子间不同的堆积模式进而得到不同的纳米形貌。四苯基卟啉分子间的强烈的π-π作用力使其聚集体形成一维的纳米带状形貌。分子间的π-π作用力和氢键的协同作用,使得化合物1其组装成纳米空心球。在化合物2的自组装过程中,除了分子间的π-π作用力和氢键的作用外,还有Cu-O金属配位键使其自组装得到一维的纳米线。这三个卟啉化合物在类似的自组装条件下,得到了不同形貌的纳米结构,这些研究结果表明非共价键尤其是π-π堆积、氢键和金属配位键的协同作用在调节和控制卟啉分子自组装纳米结构中起着非常重要的作用。这也为开发和探索新型的分子（光）电子器件的制备提供一条新的参考途径。2、三明治型混杂卟啉酞菁三层稀土金属配合物的设计、合成和自组装纳米结构的研究共轭分子体系自组装形成的各种不同结构稳定且复杂有序的纳米聚集体主要是通过分子间π-π键和其它非共价键的协同作用所得到的。所以,人们通常在共轭分子体系周围引入不同的功能基团来改变共轭分子的结构或者引入不同的非共价键来调节它们之间的作用进而调节自组装纳米结构的形貌。三明治型混杂卟啉酞菁稀土金属配合物由于在材料科学方面的应用引起了人们广泛和深入的研究兴趣。在这类化合物中,因为每个分子都有两到三个四吡咯环,并且每个四吡咯环上都有机会引入多样取代基,这样就大大增加了调节分子间作用力的可能性。所以,研究三明治型混杂卟啉酞菁稀土金属配合物的自组装过程对于它们在更多实际方面的应用提供理论价值。在本文中,我们首次详细的描述了一系列新型的三明治型混杂卟啉酞菁三层铕配合物的设计、合成、表征、以及它们的自组装性质。把不同数量或者相同数量不同位置的羟基引入到三明治型卟啉酞菁三层铕配合物卟啉的meso位苯环的对位上,在它们自组装过程中π-π堆积作用和由羟基提供的氢键的竞争和协同作用使得分子间不同的堆积模式进而得到不同的纳米形貌。在化合物1和2中,三明治分子间起到主导作用的π-π堆积作用,该作用力使其分别组装成纳米叶和线状形貌。在化合物4和5中,三明治分子间起到主导作用的是垂直于π-π堆积方向上的氢键,该作用力使其分别组装成弯曲的纳米带和球状形貌。然而,在化合物3中,氢键和π-π相互作用力的平衡使得化合物3组装成纳米带。本文工作不仅首次研究了分子结构和由其自组装得到相应的纳米结构之间的关系,而且对于通过分子设计和合成得到可控的分子堆积模式和纳米形貌有着很好的指导作用。3、酚氧基和酚硫基在双层稀土酞菁配合物体系中取代基效应的研究关于酚氧基或者酚硫基的电子性质已经成为大家争论的焦点。一般情况下,人们认为它们是类似与烷氧链和烷硫基链的供电子基,但是有时它们也可以作为吸电子基。在本文中,我们制备和表征了一系列酚氧基和酚硫基取代的的镧系双层酞菁配合物,电化学性质研究表明把八个酚氧基或者酚硫基引入到双层酞菁的周围后,使得化合物稍微的难于氧化但是易于还原,类似于化合物自由的H₂Pc（OPh）₄和H₂Pc（OPh）₈,表现出吸电子的性质。这一结论也被它们相应的自由酞菁基于前线分子轨道能量计算所支持。更多还原

【Abstract】 Owing to the unique optical,electrical,and properties,associated with the intriguing intramolecularπ-πinteractions,porphyrins,phthalocyanines,as well as sandwich type rare complexes,as a novel functional materials,have been expected to be widely potential application in materials science,such as in molecular electronics,molecular information storage,and nonlinear optics,etc.Recently,it is significantly interested in ordered supramolecular aggregate and nanoscale assembly fields.However,it must be pointed out that self-assembly of functional molecules into a prerequisite nanostructure with desirable dimension and morphology via controlling and optimizing inter-molecular interaction still remains a great challenge for chemists and material scientists.In order to extensively investigate supramolecular aggregation behaviors and supramolecular assembly methodology of porphyrinato and/or phthalocyninato complexes,in this thesis a series of porphyrin and/or phthalocyanine derivatives are selected,and some modern measuring techniques were performed to examine their aggregate structures,morphologies and nanostructures.Our research work has been focused on the following respects:1.Tuning the Morphology of Self-Assembled Nanostructures of Amphiphilic Tetra（p-hydroxyphenyl）Porphyrins with Hydrogen Bonding and Metal-Ligand Coordination BondingTypical amphiphilic metal free tetrakis（4-hydroxyphenyl）porphyrin H₂THPP（1） and tetrakis（4-hydroxyphenyl）porphyrinato copper complex CuTHPP（2） were fabricated into organic nanostructures by a phase-transfer method.Their self-assembly properties in aqueous solution have been comparatively studied with those of tetra（phenyl）porphyrin H₂TPP（3） by electronic absorption and Fourier transform infrared（FT-IR） spectroscopy, transmission electronic microscopy（TEM）,scanning electronic microscopy（SEM）,and X-ray diffraction（XRD） techniques.Experimental results reveal different molecular packing models in these aggregates,which in turn result in the self-assembled nanostructures with different morphology from nano-scale hollow spheres for 1,nanoribbons for 2,and to nanobelts for 3.The present study,representing part of our continuous efforts towards understanding the relationship between synergistic interplay among noncovalent interactions such as the n-n interaction,metal-ligand coordination bonding,and hydrogen bonding on controlling and tuning the morphology of self-assembled nanostructures of tetrapyrrole derivatives,will provide information helpful on preparing self-assembled nanostructures with controlled molecular packing conformation and morphology through molecular modification.2.Morphology Controlled Self-assembled Nanostructures of Sandwich Mixed （Phthalocyaninato）（porphyrinato） Europium Triple-deckers.Effect of Hydrogen Bonding on Tuning the Inter-molecular InteractionA series of five novel sandwich-type mixed（phthalocyaninato）（porphyrinato） europium triple-decker complexes with different number of hydroxyl groups at the meso-substituted phenyl groups of porphyrin ligand 1-5 have been designed,synthesized,and characterized. Their self-assembly properties,in particular the effects of the number and positions of hydroxyl groups on the morphology of self-assembled nanostructures of these triple-decker complexes,have been comparatively and systematically studied.Competition and cooperation between the inter-molecularπ-πinteraction and hydrogen bonding in the direction perpendicular to theπ-πinteraction direction for different compounds were revealed to result in nanostructures with different morphology from nano-leafs for 1, nano-fibbons for 2,nano-sheets for 3,curved nano-sheets for 4,and to spherical shapes for 5. The IR and X-ray diffraction（XRD） results reveal that in the nanostructures of triple-decker 2 as well as 3-5,a dimeric supramolecular structure was formed through an intermolecular hydrogen bond between two triple-decker molecules,which as the building block self-assembles into the target nanostructures.Electronic absorption spectroscopic results on the self-assembled nanostructures reveal the H-aggregate nature in the nano-leafs and nano-ribbons formed from triple-deckers 1 and 2 due to the dominantπ-πinter-molecular interaction between triple-decker molecules,but J-aggregate nature in the curved nano-sheets and spherical shapes of 4 and 5 depending on the dominant hydrogen bonding interaction in cooperation withπ-πinteraction among the triple-decker molecules.Electronic absorption and XRD investigation dearly reveal the decrease in theπ-πinteraction and increase in the hydrogen bonding interaction among triple-decker molecules in the nanostructures along with the increase of hydroxyl number in the order of 1-5.The present result appears to represent the first effort towards realization of controlling and tuning the morphology of self-assembled nanostructures of sandwich tetrapyrrole rare earth complexes through molecular design and synthesis.3.Lanthanide（Ⅲ） Double-Decker Complexes with Octaphenoxy- or Octathiophenoxyphthalocyaninato Ligands.Revealing the Electron-Withdrawing Nature of the Phenoxy and Thiophenoxy Groups in the Double-Decker ComplexesA series of heteroleptic and homoleptic bis（phthalocyaninato） lanthanide（Ⅲ） complexes, namely M（Pc）[Pc（OPh）₈],M[Pc（OPh）₈]₂,Eu（Pc）[Pc（SPh）₈],and Eu[Pc（SPh）₈]₂[M = Eu,Ho, Lu;Pc = unsubstituted phthalocyaninate;Pc（OPh）₈ = 2,3,9,10,16,17,23,24-octaphenoxyphthalocyaninate;Pc（SPh）₈ = 2,3,9,10,16,17,23,24-octathiophenoxyphthalocyaninate]（1-8） have been prepared.The molecular structure of Eu[Pc（OPh）₈]₂（4） has been determined by single-crystal X-ray diffraction analysis.All the new sandwich compounds have been characterized with various spectroscopic methods.Their electrochemical characteristics show that the introduction of phenoxy or thiophenoxy groups onto the peripheral positions of the phthalocyaninato ligand makes the double-decker harder to oxidize and easier to reduce.Theoretical calculations, using semi-empirical PM3 method,indicate that the change in the energy level of the frontier orbitals of these ligands induced by the electron-withdrawing substituents is responsible for these unusual electrochemical properties.更多还原