【作者】 高颖宁；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2010， 博士

【摘要】 卟啉(Por)是广泛存在于自然界中的一类有机化合物,它是生物分子叶绿素的功能组成部分,也是氧载体蛋白血红蛋白的活性位点。酞菁(Pc)是卟啉的类似物,由于周围增多了四个苯环,因而比卟啉具有更大的共轭体系。我们可以用化学方法修饰卟啉环和酞菁环,调整其性能。我们同样可以改变卟啉和酞菁的中心金属离子,得到我们所需要的功能材料。一般来讲,过渡金属可以形成单层配合物；离子半径大、配位数高的金属如稀土金属则可以生成夹心三明治型配合物；还有一些金属如锰、锌等,可以在配合物的轴向链接原子、基团及其他配合物。卟啉和酞菁配合物非同寻常的光、电、磁等性质可以应用于新型的分子导体、分子电子元器件、分子磁体等,拥有广阔的应用前景。本论文主要设计、合成了结构新颖的卟啉和酞菁配合物,并全面的研究了结构和性能间的联系；同时,为了合成目标分子,还设计了一种新的酞菁合成方法。1、卟啉分子自组装纳米结构的研究自组装是分子在基于非共价键的相互作用下自发形成有序结构的一种技术。自组装的过程是一种整体的复杂的协同作用,除了受配体自身的性质影响外,还受各种外界的物理和化学因素的影响。不同的纳米结构可以应用于不同的领域,例如：纳米空心结构可以应用于药物传输,纳米带可以作为有机半导体。近年来,有机功能分子的超分子聚集体和纳米尺度组装的研究成为了广大科研工作者研究的热点,在纳米科学与技术中获得广泛的应用。在本章中,我们设计合成了两种新颖的卟啉分子,并且利用相转移的方法在甲醇和正己烷中将它们分别制备成有机纳米聚集体：metal free5,15-di[4-(5-acetylsulfanylpentyloxy)phenyl]porphyrin H2[DP(CH3COSC5H10O)2P] (1)和5,15-di[4-(5-acetylsulfanylpentyloxy)phenyl]porphyrinato zinc Zn[DP(CH3COSC5H10O)2P](2)。利用紫外(UV)、红外(FT-IR)、核磁(NMR)、扫描电镜(SEM)、X-射线衍射(XRD)等表征手段系统研究了化合物1和2以及它们聚集体的性质。晶体结构表明,化合物2中存在Zn与O的配位作用。在氯仿中,化合物1表现为二维“气泡”；由于存在Zn-O配位作用,化合物2表现为三维“网状”。在甲醇中的自组装过程中,分子间的π-π相互作用和范德华力使得化合物1自组装成纳米球；π-π相互作用和Zn-O配位作用的竞争和协同作用使得化合物2自组装成纳米棒。在正己烷中的自组装过程中,分子间的π-π作用力和范德华力使得化合物1自组装成纳米带；π-π相互作用和Zn-O配位作用的竞争和协同作用使得化合物2自组装成纳米空心球。我们首次揭示了在宏观的晶体结构中分子排列方式和微观的自组装聚集体中分子排列方式的关系,为设计有机功能材料提供一条新的参考途径。2、两亲性三层酞菁化合物的设计合成及OFET性质研究酞菁作为一种共面的18π电子共轭大环体系非常稳定,其衍生物与其它有机半导体材料相比,具有良好的化学稳定性和热稳定性。三明治型酞菁稀土配合物具有特殊的结构,分子内酞菁环之间存在着强烈的π-π相互作用,与单层相似物相比,共轭程度有所增加。同时,由于其在有机溶剂中具有良好的可溶性以及成膜性,这类分子材料作为本征的半导体被期待在有机场效应晶体管(OFET)领域起到更重要的作用。目前,多数酞菁类器件都是用真空蒸镀的方法制作而成的。最近,以溶液为基础的薄膜沉积和印刷方法得以广泛应用。本章设计合成了以冠醚环为亲水层,烷氧链为疏水层,具有两亲性的三层三明治型酞菁配合物,并且采用Langmuir-Blodgett (LB)膜的方法,将它们制成OFET器件。我们通过改变冠醚环的大小以及对基底的处理方法,达到调控其OFET性质的目的。我们对这一系列双亲性酞菁进行了紫外、红外和元素分析等完整的表征,研究了其电化学性质及OFET性质,揭示了在这种两亲性三层酞菁化合物中冠醚环的大小和不同的基底处理方法与场效应迁移率和开关比之间的关系,并详细阐释了原因。3、α位取代酞菁分子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的纳米聚集体主要是通过分子间π-π相互作用和其它非共价键的协同作用所得到的。人们通常在共轭分子体系引入不同的功能基团或者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。酞菁具有大的π共轭体系,良好的热稳定性,易于裁剪和衍生等性质,已经在超分子自组装体系的研究中引起了高度的重视。本章设计合成了两种新颖的α位取代酞菁分子：metal free1,4,8,11,15,18,22,25-octa(butyloxy)phthalocyanine H2Pc(α-OC4H9)8 (1)和1,4,8,11,15,18,22,25-octa(butyloxy)phthalocyaninato lead Pb[Pc(α-OC4H9)8] (2)。我们采用相转移的方法将它们制备成有机纳米聚集体。晶体结构证明化合物1具有马鞍状的构型,化合物2则以伪双层的形式存在。从SEM图片中可以看到,在没有钠离子存在的情况下,1和2分别形成尺寸不同纳米带；在钠离子存在的情况下,1和2分别形成扭曲的纳米带,并且尺寸进一步发生变化。我们利用它们良好的结晶性,系统的探讨组装过程的机理、动力学以及热力学过程；我们还利用它们特殊的分子结构,研究钠离子的作用,以及其所形成的配位键对自组装过程的影响。4、α位取代酞菁对称双层化合物合成及性质的研究双层酞菁稀土配合物具有特殊的光、电、磁等性质,可以应用于气体传感器、场效应晶体管以及分子磁体等。目前对双层酞菁化合物的研究主要集中在没有取代或者β位取代的酞菁双层,而对α位取代酞菁双层的研究相对较少。由于巨大的空间位阻,α位八取代酞菁双层一直被认为是无法合成的。本章选择变形严重的metal free 1,4,8,11,15,18,22,25-octa(butyloxy)phthalocyanine H2Pc(α-OC4H9)8作为起始原料,利用催化和模板的方法,成功得到了三明治型化合物HMⅢ[Pc(α-OC4H9)8]2 [M=Eu (1), Y (2); Pc(α-OC4H9)8=1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyanine]。我们通过一系列平行实验,证明了1,8-二氮杂环[5,4,0]十一烯-7(DBU)的催化作用,并详细讨论了DBU的催化机理和不同冠醚的模板作用；同时选择不同的金属,证明了该方法的普遍性,对卟啉酞菁类化合物的合成具有重大意义。更多还原

【Abstract】 Porphyrins are a group of organic compounds that frequently occur in nature. The porphyrin structure is the functional composition of chlorophyll, a kind of biomolecule. It is also the active site of hemoglobin, the well-known oxygen carrier protein. Phthalocyanines are analogues of porphyrins. Due to the additional 4 benzene rings on the periphery, they are more conjugated. Both series belonging to a cyclic tetrapyrrole family are able to be modified by chemical methods. At the same time, different metal atoms can also change the functions. Generally, with the help of transition metals, metal tetrapyrrole complexes can be obtained. While with large metal centers and high coordination numbers, sandwich-type double-and triple-deckers complexes can be formed. Special metal centers such as Mn and Zn can also induce axial coordination. Owing to the extraordinary optical, electrical, and magnetic properties, porphyrins, phthalocyanines, as well as their sandwich-type double-and triple-decker structures have been recently emerging as advanced molecular materials with great potential applications in the fields of molecular conductors, molecular electronics, molecular magnets, etc. In this thesis a series of porphyrin and/or phthalocyanine derivatives are designed, with their structures and properities comprehensively studied. Moreover, a new method for the synthesis of phthalocyanine was involved. Our research work has been focused on the following respects:1. Morphology-Controlled Self-Assembled Nanostructures of 5,15-Di[4-(5-acetylsulfanylpentyloxy)phenyl]porphyrin Derivatives. Effect of Metal-Ligand Coordination Bonding on Tuning the Intermolecular InteractionNovel metal free 5,15-di[4-(5-acetylsulfanylpentyloxy)phenyl]porphyrin H2[DP(CH3COSC5H10O)2P] (1) and its zinc congener Zn[DP(CH3COSC5H10O)2P] (2) were designed and fabricated into organic nanostructures by a phase-transfer method. Their self-assembling properties in MeOH and n-hexane were comparatively investigated by scanning electronic microscopy (SEM) and X-ray diffraction (XRD) technique. Inter-molecularπ-πinteraction of metal free porphyrin 1 leads to the formation of hollow nanospheres and nanoribbons in MeOH and n-hexane, respectively. In contrast, introduction of additional Zn-O coordination bond for porphyrinato zinc complex 2 induces competition with inter-molecularπ-πinteraction, resulting in nanostructures with nanorod and hollow nanosphere morphology in MeOH and n-hexane. The present result appears to represent the first effort towards controlling and tuning the morphology of self-assembled nanostructures of porphyrin derivatives via molecular design and synthesis through introduction of metal-ligand coordination bonding interaction. Nevertheless, availability of single crystal and molecular structure revealed by X-ray diffraction analysis for both porphyrin derivatives renders it possible to investigate the formation mechanism as well as the molecular packing conformation of self-assembled nanostructures of these typical organic building blocks with large conjugated system in a more confirmed manner.2. Design, Synthesis, Characterization, and OFET Properties of Amphiphilic Heteroleptic Tris(phthalocyaninato) Europium(III) Complexes. The Effect of Crown Ether Hydrophilic SubstituentsTwo amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)4]Eu[Pc(mCn)4]Eu[Pc(OC8H17)8] (m=12, n=4; m=18, n=6) (1,2) were designed and prepared. These novel sandwich triple-decker complexes have been characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of Langmuir-Blodgett (LB) technique, these typical amphiphilic triple-decker complexes have been fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO2/Si substrate, hexamethyldisilazane (HMDS)-treated SiO2/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO2/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. The carrier mobility for hole as high as 0.33 cm2 V-1 s-1 and current modulation of 7.91×105 have been reached for the devices of triple-decker compound 1 deposited on the octadecyltrichlorosilane (OTS)-treated SiO2/Si substrates, indicating the effect of substrate surface treatment on the OFET performance due to the improvement on the film quality as demonstrated by the atomic force microscope (AFM) investigation results. 3. Nonperipherally Octa(butyloxy)-substituted Phthalocyanine Derivatives with Good Crystallinity. Effect of Metal-Ligand Coordination on the Molecular Structure, Internal Structure, and Dimension of Self-Assembled NanostructuresTo investigate the effect of metal-ligand coordination on the molecular structure, internal structure, dimension, and morphology of self-assembled nanostructures, two non-perpherally octa(alkoxyl)-substituted phthalocyanine compounds with good crystallinity, namely metal free 1,4,8,11,15,18,22,25-octa(butyloxy)phthalocyanine H2Pc(a-OC4H9)8 (1) and its lead complex Pb[Pc(α-OC4H9)8] (2), were designed and synthesized. Single crystal X-ray diffraction analysis reveals the distorted molecular structure with a saddle conformation for 1 and a Pb-connected pseudo-double-decker supramolecular structure with a domed conformation for 2, respectively. The formation of nanoribbons in the absence of Na+ with ca. 100 and 150 nm average width for 1 and 2, respectively, revealed the molecular structure (conformation) associated with metal-ligand (Pb-Nisoindole, Pb-Naza, and Pb-Obutyloxy) coordination on the dimension of nanostructures for 2. The formation of twisted nanoribbons in the presence of Na+ with ca.50 and 100 nm average width for 1 and 2, respectively, revealed the molecular structure (conformation) associated with additional metal-ligand (Na-Naza and Na-Obutyloxy) coordination bonds for both the compounds. Both nanoribbons and twisted nanoribbons display rich higher order refraction peaks in their XRD patterns, giving clear information about the internal structure of the nanoribbons. To the best of our knowledge, the present result represents the first self-assembled nanostructures fabricated from phthalocyanine derivatives with confirmed internal structure, controllable dimension and morphology, and high molecular ordering nature. It will be helpful for the design and preparation of phthalocyanine-based nanoelectronic and nanooptoelectronic devices with good performance due to the close relationship between molecular ordering and dimension of nanostructures and the performance and size of nanodevices.4. Bis[1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyaninato] Rare Earth Double-Decker Complexes:Synthesis, Spectroscopy, and Molecular StructureHomoleptic octa-α-substituted bis(phthalocyaninato) rare earth sandwich-type complex HMⅢ[Pc(α-OC4H9)8]2 [M=Eu(1), Y(2)] have been prepared in the presence of organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and benzo-18-crown-6/benzo-15-crown-5 in refluxing n-octanol. To the best of our knowledge, it is the first example of homoleptic non-peripherally octa(alkoxyl)-substituted bis(phthalocyaninato) rare earth complexes. Comparative studies on a series of reactions reveal the key role of DBU as catalyst and crown ether as template in the formation of homoleptic rare earth double-decker complexes with structurally highly deformed non-peripherally octa(butyloxy)-substituted phthalocyanine ligand. The molecular structure of the complex 1 has been determined by single-crystal X-ray diffraction analysis. The metal center is octa-coordinated by the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. These two bis(phthalocyaninato) rare earth double-deckers have also been characterized by a wide range of spectroscopic methods including MS,1H NMR, UV-vis, IR, and EPR. Structural and spectroscopic studies reveals that theπ-πinteraction between the two Pc(a-OC4H9)g rings is weaker than that for the corresponding unsubstituted orβ-substituted bis(phthalocyaninato) analogues.更多还原