【作者】 李仁杰；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2008， 博士

【摘要】 酞菁（Pc）作为一种共面的18π电子共轭大环体系被证实与自然界存在的卟啉十分类似。酞菁的一个显著的特性是它的多功能性和可剪裁性，通过在酞菁环上进行一些化学修饰，可以很好的调整其性能。其大环周围苯环上的每一个位置均可以被取代基所取代，而且，取代基的位置和种类大大影响着酞菁的物理和化学性质。中心金属离子同样影响到酞菁的结构和物化性能，对于过渡金属，一般形成单层酞菁配合物，而离子半径较大、配位数也较大的一些金属如稀土金属却以夹心三明治型配合物的形式存在。近年来，酞菁配合物以其非同寻常的光、电、热、磁性质和作为新型的分子导体、分子磁体、分子电子元器件等功能材料的巨大的应用潜力，吸引着人们越来越浓厚的研究兴趣。而怎样去寻找一个有着新颖性质的结构一直是困扰人们的难题，本论文主要就这种有着优异剪裁性的酞菁类化合物的研究来寻找结构和性能间的联系，并尝试设计合成了一些具有预期性质的酞菁类化合物并对其进行了深入的研究。1、酞菁体系中取代基效应的研究酞菁（Pc）大环周围的苯环上的每一个位置均可以被取代基所取代，所以在酞菁环上一共有16个可取代的位置。其中1，4，8，11，15，18，22，25被称为非周边位置（np-site）或α位；2，3，9，10，16，17，23，24称为周边位置（p-site）或β位。其中取代基的位置和种类大大影响着卟啉、酞菁的物理和化学性质。由于分子间较强的相互作用，绝大多数未取代酞菁及其金属配合物在水和有机溶剂中难以溶解，因而限制了它们的应用研究。若在酞菁分子上引入取代基，尤其是具有较大空间阻碍的取代基，则可以有效地阻碍分子之间的聚集，提高其在有机溶剂中的溶解度。除此之外，引入不同的取代基还可以调变酞菁的性质，使之更加适应作为特定材料的需要。本章重点研究了各种不同取代基，不同取代位置的自由酞菁的电化学性质。实验结果表明：烷基，烷硫基在自由酞菁的边缘位置取代对酞菁体系的电化学基本没有影响。烷氧基无论是在α位还是β位都作为给电子基团出现，而酚硫基则与炔基一样均为吸电子基团。酚氧基的情况比较特殊，随着酚氧基的加入，第一氧化电位增大而第一还原电位减小。为了加深对酞菁体系中取代基效应的理解，我们使用PM3算法对各种取代自由酞菁的分子轨道（MO）进行了模拟计算，研究了分子轨道（MO）与其电化学性质间的内在关系。2、酞菁体系中π共轭效应的研究酞菁具有特殊的二维共轭π-电子结构，共轭的大环体系有强烈的π-π电子相互作用，这是该类化合物具有特殊的光、电、磁学等特殊性质的结构基础。尽管与酞菁相比研究的比较少，其环扩展和收缩的类似物，即萘菁（Nc）和四氮杂卟啉（TAP），近年来也引起了越来越多的注意。为对这些酞菁类化合物的性质获得更深入的理解，本章设计合成了两种办法改变酞菁的π共轭体系。一种是平面扩展或收缩酞菁大环来改变其π体系大小；另一种是将酞菁大环立体化，制备成三明治型的酞菁双层和π共轭体系更大的萘菁的双层。研究结果表明随着平面π共轭体系的增大，化合物的紫外可见光谱和荧光光谱中最大吸收或激发波长均逐步红移。电化学中第一氧化电位与第一还原电位及第一氧化和还原的电势差均逐步减小。同时可以看出外围苯环单元的取代基效应小于内侧苯环的取代基效应。对于立体化的酞菁双层和萘菁双层，第一氧化和第一还原过程的半波电位，随着稀土原子半径的减小而轻微地线性地向负方向移动。化合物的第二和第三氧化电位则恰恰相反，随着稀土原子半径的减小线性增大。第二还原到第四还原电位则几乎不随稀土原子半径的变化而变化。比较萘菁双层和酞菁双层还发现，环共轭体系的增大在一定程度上会削弱金属大小对配合物的影响。3、一种具有特殊超分子结构的酞菁锌的设计合成酞菁由于其大的π共轭体系，良好的热稳定性，易于裁剪和衍生等性质，在超分子体系的研究中早就被人们所重视。除了取代基和中心金属外，排列方式特别是晶体中分子的排列方式也是影响酞菁性质的重要因素。从二十世纪八十年代起，人们广泛研究了具有各种取代基和各种中心金属的酞菁配合物的晶体结构和性质。尽管人们试图在晶体中将酞菁体系直接使用氢键连接形成面对面堆积的形式，但除IIA的Mg和Be外，由于酞菁分子间很强的π-π相互作用，水很难插入两个酞菁大环之间与金属配位，使得由中心金属配位水的氢键连接的具有面对面超分子结构的酞菁体系很难实现。本章通过设计合成完成了这个难题，并对这种由氢键连接的伪三明治型的锌酞菁进行了完整的表征和电化学性质研究，并从晶体结构入手辅以理论计算解释了这种具有C₄对称性的α位烷氧基四取代锌酞菁进行这样一种特殊超分子组装的内在原因。4、一系列双亲性酞菁的设计合成及OFET性质研究由于酞菁衍生物与其它有机半导体材料相比有着良好的化学稳定性和热稳定性，其薄膜被广泛用作场效应晶体管（FET）的组成部分。大多数以酞菁为材料的器件都是用真空蒸镀的方法制作的。近年来，以溶液为基础的薄膜沉积（如旋转涂膜、分子自组装膜和LB膜）以及印刷方法作为公认的低成本制备方法，引起人们越来越多的关注。众所周知，双层酞菁稀土配合物在普通有机溶剂中具有良好的可溶性以及成膜性，而且由于其特殊的三明治结构，分子内酞菁环之间存在着强烈的π-π相互作用，人们期待以这类分子材料作为本征的半导体比其单层相似物在有机场效应晶体管（OFET）领域起到更重要的作用。本章设计合成了以氧乙烯链为亲水层，烷氧链为疏水层，具有双亲性的三层三明治型酞菁配合物。通过改变烷氧链的长度来改变配合物的双亲性，以期达到调整膜的组成而调控其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、质谱和元素分析等完整的表征，研究了其电化学性质，并使用LB膜沉积的方法制备了有机场效应晶体管并研究了它们的场效应迁移率，揭示了在这种带有开链冠醚的三层酞菁化合物中烷氧链的长度和场效应迁移率之间的关系，并阐释了其内在原因。更多还原

【Abstract】 Phthalocyanines and porphyrins are two important classes of pigments which have found their applications in various disciplines. Both series belong to a cyclic tetrapyrrole family in which the four isoindole or pyrrole nitrogen atoms are able to complex with a range of metal ions. With large metal centers which favor octa-coordination （e.g. rare earths, actinides, group 4 transition metals, and main group elements such as In, Sn, As, Sb, and Bi）, sandwich-type complexes in the form of double- and triple-deckers can be formed. Due to the intramolecularπ-πinteractions and the intrinsic nature of the metal centers, these novel complexes display characteristic features, which cannot be found in their non-sandwich counterparts, enabling them to be used in different areas. They are versatile materials for electrochromic displays, field effect transistors, gas sensors and as structural and spectroscopic models for the special pair found in the bacterial photosynthetic reaction centers.Our research work has been focused on the following respects:1. The Electron-donating or -withdrawing Nature of Substituents Revealed By the Electrochemistry of Metal-free PhthalocyaninesThe effect of substituents on the electrochemistry of metal-free phthalocyanines was examined for seventeen phthalocyanine compounds, which also provides new information about the electronic donating or withdrawing nature of various substituents, namely alkoxy. alkylthio, alkyl, alkynyl, phenyloxy, and phenylthio groups attached onto the phthalocyanine system, from the viewpoint of electrochemistry. Most of the effects of peripheral and non-peripheral substitution on the electrochemistry of metal-free phthalocyanines have been reasonably explained by considering the energy levels of frontier molecular orbitals of corresponding compounds, which were obtained by the calculations using semi-empirical PM3 method.2.Study ofπ-conjugated Systems in Ring-Fused Phthaloyanine Derivatives and Bis-（na）pthalocyaninato Double-decker ComplexesWe have prepared a series of Pc derivatives with variousπ-conjugated systems by fusing benzo rings and quantitatively characterized the electronic structures. The LUMO and HOMO were found to have a parallel relationship. The shift of the redox potentials, and the relationship between the frontier orbitals and fused benzo rings were quantitatively characterized in terms of the CV measurements and MO calculations. Moreover, the electrochemistry of homoleptic bis（naphthalocyaninato） double-decker complexes for the whole series of tervalent rare earths M（TBNc）₂ has been systematically studied by cyclic voltammetry （CV） and differential pulse voltammetry （DPV）. The half-wave potentials of all the oxidations and the first reduction for double-decker complexes are dependent on the size of the metal center. The difference between the redox potentials of the first and second reductions for M^Ⅲ（TBNc）₂, which represents the potential difference between the first oxidation and first reduction of [M^Ⅲ（TBNc）₂]^-, lies in the range 1.09-0.95 V and gradually diminishes along with the lanthanide contraction, indicating increasedπ-πinteraction in the double-deckers in the same order. Comparison of electrochemical characteristics between M（TBNc）₂ and M（TBPc）₂ reveals that the extension on the ligand conjugated system from phthalocyanine to naphthalocyanine attenuates the ring-to-ring separation effect on the redox potentials of the double-deckers of the whole series of tervalent lanthanides.3. H₂O-involved hydrogen bonds in pseudo double-decker supramolecular structure of phthalocyaninato zinc complex1,8,15,22-Tetrakis（3-pentyloxy）phthalocyaninato zinc complex Zn[Pc(α-OC₅H₁₁)₄] has been prepared by treating metal-free phthalocyanine H₂Pc(α-OC₅H₁₁)₄ with Zn（OAc）₂·2H₂O in refluxing n-pentanol. X-ray single crystal analysis reveals that two water molecules exist between two Zn[Pc(α-OC₅H₁₁)₄] molecules. Each H₂O coordinates with one zinc cation and hydrogen bonds with an aza-nitrogen atom and its neighboring oxygen atom from the alkoxy substituent of another molecule, forming a pseudo-double-decker supramolecular structure in the crystals with a ring-to-ring separation of 3.728 A. This, to the best of our knowledge, represents the first example of phthalocyaninato transition metal complexes, for which the H₂O-involved hydrogen bonds connect two phthalocyanine rings to form a pseudo-double-decker supramolecular structure {Zn[Pc(α-OC₅H₁₁₄]·H₂O}₂. To enhance understanding the existence of hydrogen bonds in the solid state crystal structure of this compound, theoretical calculations on the stabilization energy in a system composed of two Zn[Pc(α-OC₅H₁₁)₄] moieties as well as in the supramolecular structure {Zn[Pc(α-OC₅H₁₁4]·H2O}2 have been performed using the density functional theoretical method. Comparison in the calculated stabilization energy between these two systems together with the nature bond orbital analysis over the later supramolecular structure reveals the dominant H2O-involved hydrogen bonding interaction over theπ-πinteraction in {Zn[Pc(α-OC5H11)4]·H2O}2.4. Synthesis, Characterization, and OFET Properties of Amphiphilic Heteroleptic Tris（phthalocyaninato） Europium（Ⅲ） Complexes with Hydrophilic Poly（oxyethylene） SubstituentsA series of amphiphilic heteroleptic tris（phthalocyaninato） europium complexes with hydrophilic poly（oxyethylene） heads and hydrophobic alkoxy tails {Pc[（OC2H4）2OCH+3]8}Eu{Pc[（OC2H4）2OCH3]8}Eu[Pc(OCnH2n+1)8] （n = 6, 8, 10, 12） （1-4） were designed and prepared from the reaction between homoleptic bis（phthalocyaninato） europium compound {Pc[（OC2H4）2OCH3]8}Eu{Pc[（OC2H4）2OCH3]8} and metal free 2,3,9,10,16,17,23,24-octakis（alkoxy） phthalocyanine H2Pc(OCnH2n+1)8 （n = 6, 8. 10,12） in the presence of Eu（acac）3·H2O （Hacac = acetylacetone） in boiling 1,2,4-trichlorobenzene （TCB）. 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 unusual bottom contact configuration. The devices display good OFET performance with the carrier mobility for holes in the direction parallel to the aromatic phthalocyanine rings, which shows dependence on the length of hydrophobic alkoxy side chains, decreasing from 0.46 for 1 to 0.014 cm² V^-1 s^-1 for 4 along with the increase in the carbon number in the hydrophobic alkoxy side chains.</sub>更多还原