【作者】 盛宁；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2008， 博士

【摘要】 随着科技的发展及生产生活的需要,对于功能性新材料的开发与应用已经成为当前研究的重要任务和热点问题。人们正致力于开发与创造能与天然材料媲美甚至优于天然材料的新的功能材料。自从人们认识到卟啉衍生物在生命历程中的重要性后,对于其结构、功能及性质的研究至今依然是研究的热点;而酞菁化合物良好的催化及光电特性引起了人们浓厚的研究兴趣,其作为新型功能材料不断得到开发和利用。卟啉、酞菁这类大环分子独特的结构及光、电、热、磁等特性己吸引了众多学者从事该领域的研究。所有工作都是围绕对大环进行裁剪、修饰及组装等进行的。制备三明治型卟啉、酞菁化合物也是手段之一。在三明治型化合物中,两个或三个卟啉和/或酞菁(包括萘菁)大环配体被一个或两个稀土离子配位,形成高度共轭的三明治夹心结构,大环被稀土离子拉至一个很近的距离(约3.5A),体系间存在强烈的π—π电子相互作用。未配对电子在化合物中的离域,使化合物显示出独特的物理和化学性质。作为分子半导体、光导、光电材料、光限幅、非线性光学、气体传感、电致变色、分子磁体和液晶等功能材料具有极大的应用潜力。本课题组多年来一直致力于稀土卟啉、酞菁三明治化合物的合成。一方面努力探索和开发更加简单有效的合成方法来制备带有不同取代基修饰的卟啉酞菁三明治型配合物;另一方面,在性质研究领域也有很多开拓性工作,如三明治型化合物的光物理及电化学性质、有机场效应晶体管性质以及超分子组装的研究。本文的研究工作主要集中在以下几个方面:1.冠醚取代不对称双层和单层酞菁的合成、表征及超分子组装的研究设计合成超分子体系,在生物科学方面已有重大的发展,在材料科学和电致变色方面的潜在应用价值对化学和材料学家都是一个很大的挑战。近一个世纪以来,酞菁作为新型分子导体、分子磁体、分子电子元器件、光限制、非线性光学、气体传感、电致变色,光电转换和液晶等功能材料被深入研究。另一方面,由于对碱金属,碱土金属离子的特殊选择络合作用,冠醚被大量的合成和研究,也是目前世界上分子识别,分子组装领域内的热点研究课题。为了寻求新奇的具有多功能性质的超分子构造,自上世纪八十年代以来,将冠醚的识别作用和自组装能力与酞菁的功能性相结合,吸引了许多学者并激起了广泛的研究热潮。我们使用模板法合成并成功分离了一系列冠醚取代的双层不对称酞菁,包括含有一个、两个(邻位和对位)、三个和四个冠醚取代的双层不对称酞菁,其中两个及三个冠醚取代的酞菁是由本课题组首次合成并分离的。另外,我们采用了一种新颖的合成方法首次成功制备了一系列不同数目(1-4)冠醚取代的不对称酞菁铜,即以上述制备的双层不对称酞菁为原料,将双层拆分成两种单层化合物,根据溶解性的不同将它们一一分离。上述两个系列的酞菁化合物在提纯后得到了满意的元素分析结果。这些配合物使用紫外可见、近红外、红外光谱和质谱明确地推断出来。另外还系统研究了它们与钾离子进行超分子组装的过程。2.四卟啉—芘低聚物的合成、表征及三阶非线性性质的研究双卟啉及其低聚卟啉的应用前景是十分诱人的,它们可以应用于模拟光合作用体系,如模拟光合作用的反应中心或捕集太阳能的天线系统,制备以卟啉为母体的分子器件,这也是分子电子学工程的一部分。同时,作为三阶非线性材料的有利候选者,关于卟啉及其衍生物的非线性光学性质也被广泛的研究。我们采用无铜条件下的钯催化偶合法,首次合成了以乙炔键连接的四卟啉—芘低聚物,同时还合成了四锌卟啉—芘低聚物。这两种新制备的低聚卟啉化合物在提纯后使用紫外可见、核磁、元素分析和质谱明确地表征出来。另外,我们还研究了分子内的能量转移过程,并使用Z扫描方法研究了这个体系的三阶非线性性质。3.四芘取代的卟啉酞菁三明治型化合物的合成及表征由于三明治型酞菁稀土配合物的共轭大环之间强烈的π-π电子相互作用,引起的独特的光、电、磁等物理性质,其在过去的几十年间作为新型分子导体、分子磁体、分子电子元器件、光限制、非线性光学、气体传感、电致变色、光电转换和液晶等功能材料被深入研究。卟啉酞菁都是易于修饰的功能大环,将同样具有功能特性的其它化合物与之相连就可以合成更具多功能性质的化合物。在本文中,我们将荧光基团芘连接在卟啉的四个meso位上,并使用模板诱导法首次合成了四芘取代的卟啉酞菁混杂的双层和三层三明治型化合物。上述卟啉酞菁化合物在提纯和重结晶后得到了满意的元素分析结果。这些配合物使用紫外可见、近红外、红外光谱和质谱明确地推断出来。同时我们还探讨了这三种化合物分子内能量传递和电子转移过程。更多还原

【Abstract】 With the development of science and technology,the investigation and application of new functional materials have been the main task for production and life.People are pursuing for discovering and developing new functional man-made systems that can competent with the natural systems.After having known the significance of the porphyrins and their derivatives involved in the most important processes of natural lives,the structures,properties,and functions of the porphyrin complexes have always been the key points of the research work and discussion.Phthalocyaninato complexes,a kind of compounds that have the same structures with those of porphyrins,which are widely used as industral commodities from their first discovery in the beginning of last century,have triggered wide interests in developing their catalistic and photo-electric properties as the new functional materials recently.The tetrapyrrolic macrocyclic molecules such as porphyrin and phthalocyanine with unique photonic,electronic,and magnetic properties as well as their stabilites in air deduced from their particular structures,have attracted a lot of researchers devoting themselves to this field.Most of the work involves the modification and assembling of the macrocycles.Preparation of the porphyrinato and/or（na）phthalocyaninato sandwich-type complexes is one kind of useful method among them.Two or three porphyrin and/or （na）phthalocyanine ligands are coordinated with one or two rare earth metal ions to form the highly conjugated sandwich type double- or triple-decker complexes.Strongπ-πinteractions between the maerocyeles induces remarkable physical and chemical properties of these complexes,therefore,to provide anticipated candidates as molecular semiconductor,photo conductor,optical materials,optical limiting,non-linear optical materials,gas sensors,electrochromic materials,molecular magnetics,and liquid crystal materials.During the past several years,our research group had paid our attention to synthesize the porphyrin and phthalocyanine rare earth sandwich complexes.On one hand,we have been aiming to develop effective synthetic routes and methods towards preparing the porphyrin and phthalocyanine ligands with different peripheral substitutes,on the other hand to exploit the physic-chemial properties,organic field effect transistor（OFET）functionalities, and supramolecular assembling nature.With our continuous efforts,we have prepared a series of symmetrical and unsymmetrical sandwich-type double- and triple-decker complexes.In this dissertation,our research work has been focused on the following respects: 1.Bis（phthalocyaninato）europium（Ⅲ）double-decker complexes and phthalocyaninato copper（Ⅱ）complexes fused with different number of 15-crown-5 moieties:synthesis, spectroscopy,supramolecular structures,and the effects of substituent number and molecular symmetryThe design and preparation of supramolecular structures,which have been inspired by the significant progress in biological science and the many important potential applications in material science and molecular electronics,are great challenges for chemists and material scientists.Phthalocyanine has been an important class of dyes and pigments since their fast synthesis early last century.In particular,bis（phthalocyaninato）rare earth complexes have been intensively studied as advanced materials for gas sensors, electrochromic displays,photoconductors,and molecular electronics.On the other hand, crown ethers that have remarkable recognition and metal binding properties have been found wide applications also in molecular electronic devices.The combination of these two functional subunits for the purpose of constructing novel supramolecular structures with new and multi-functional properties has stimulated wide research interest.In this paper,we reported the synthesis,spectroscopy,supramolecular structures of a series of heteroleptic bis（phthalocyaninato）europium（Ⅲ）complexes with one,two,three, and four 15-crown-5 voids attached at different positions of one of the two phthalocyaninato ligands:Eu（Pc）（Pc’）[Pc’= Pc（15C5）,Pc（opp-15C5）₂,Pc（adj-15C5）₂, Pc（15C5）₃,Pc（15C5）₄];The other series of phthalocyaninato copper compounds CuPc（15C5）n（n = 1-4）is also been prepared employing a novel methodology using heteroleptic bis（phthalocyaninato）rare earth complexes Eu（Pc）（Pc’）[Pc’ = Pc（15C5）, Pc（opp-15C5）₂,Pc（adj-15C5）₂,Pc（15C5）₃,Pc（15C5）₄]as starting material,reaction with copper acetate in large excess amount provides two different kinds of phthalocyaninato copper compounds Cu（Pc）and CuPc（15C5）_n（n = 1-4）in relatively good yields.Having a series of closely related phthalocyanines with different number and / or disposition of 15-crown-5 groups at the peripheral positions,the effects of 15-crown-5 substituent number and molecular symmetry on the electronic absorption spectra,infra-red（IR） spectra,and supramolecular structure formation induced by K⁺ ions have been investigated.Systematic studies over the formation of dimeric supramolecular structures of the series of monomers reveal and confirm the previously proposed two-step three-stage process of K⁺-induced dimerization of phthalocyanines with three or four 15-crown-5 moieties.2.Synthesis,characterization and third-order nonlinear optical property of novel ethynyl linked heteropentamer composed of four porphyrins and one pyreneOrganic materials,in particular,with the structure of extensively delocalized z-electrons have received significant attention recently due to their large NLO susceptibilities, architectural flexibility,and ease of fabrication.Since porphyrins are promising candidates for nonlinear optical materials in view of not only largeπ-conjugated systems but also versatile functionalization at the peripheral positions and various possibilities of the central metalion,the expansion of theπ-electronic network of porphyrins has been attempted previously,some porphyrin arrays which were linked by alkyne linkages or directly linked and self-assembled porphyrin oligomers have showed enhanced NLO properties.However, covalently alkyne-linked porphyrin arrays with star shaped arrangement have never been studied on their nonlinear optical properties.In fact,effective and simple synthetic pathway to alkyne-linked porphyrin arrays with well-defined arrangement has attracted great attention for many researchers.In this paper,we used Pd-mediated reactions to join iodo/ethynyl-substituted porphyrin building blocks,synthesizing novel multi-porphyrins-pyrene arrays with a star arrangement, in which four meso-tetraphenyl porphyrins were linked to the center unit of pyrene by four aeetylenyl bonds.Then we investigated their third-order nonlinear optical properties using the Z-scan method with 1064 nm laser pulses of 20 ps duration in comparison with corresponding porphyrin and pyrene monomers.3.Synthesis,spectroscopy,electrochemistry,and photophysical properties of novel sandwich europium（Ⅲ）complexes with porphyrin ligand beating four pyrenyl groups at the meso-positionsOwing to their unique optical,electrical and magnetic properties associated with the intriguing inter-ringπ-πinteractions,sandwich-type bis（phthalocyaninato）rare earth complexes have been intensively studied over the past several decades as prospective molecular electronic,molecular magnetic,electrochemical display,and non-linear optical materials.Recently,mixed（phthalocyaninato）（porphyrinato）rare earth analogues have received increasing attention partly because the individual chromophores display very different optical and redox properties which facilitate the study of theπ-πinteractions and the extent of hole delocalization.The mixed ring triple-decker complexes are also attractive for their potential use in information storage due to their large number of redox states,reversible electrochemistry,and relatively low oxidation potentials.It is well known that to tune the performance of the sandwich compounds,a good method is to introduce effective substituents onto porphyrin or phthalocyanine ring.In this paper,we devised and synthesized a novel porphyrin ligand with four pyrenyl groups at the meso-positions H2TPYRP,with which the mixed（phthalocyaninato）（porphyrinato） europium double- and triple-decker complexes Eu（Pc）（TPYRP）and Eu₂（Pc）₂（TPYRP） were prepared according to published procedure.To the best of our knowledge,these represent the first example of sandwich tetrapyrrole rare earth complexes attached directly with the excellent pyrenyl fluorophores.As a result,their photophysical properties were comparatively studied together with that for the monomeric metal free porphyrin H₂TPYRP.更多还原