【作者】 周杨；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2010， 博士

【摘要】 卟啉和酞菁是非常重要的染料分子,它们都属于环状四吡咯化合物,其中的四个吡咯或异吲哚氮原子可以和金属元素络合而形成多种多样的配合物。当配位的中心金属离子半径较大时(例如稀土元素,锕系元素以及主族元素In,Sn,As,Sb,Bi等),倾向于形成八配位的三明治型二层或三层配合物。在三明治型配合物中,由于两个或三个共轭大环配体之间距离很近,所以具有非常强的分子内π-π相互作用,这就使得这类配合物具有非常特殊的功能性质和应用前景,例如可以作为电致变色显示材料、场效应晶体管材料、气体传感材料以及光合作用反应中心特殊对的结构和谱学模型等。光学活性的四吡咯大环衍生物和许多生物学过程相关,并且具有多方面的应用潜力,因而激起了学者们极大的研究热情。近几十年来,人们对手性卟啉化合物进行了大量的研究,主要集中在对自然界中存在的卟啉衍生物的结构和功能模拟上,而对手性酞菁衍生物的研究报道是最近才出现的。本文的研究内容就主要集中在手性共轭四吡咯大环化合物的合成、表征及拆分研究方面,包括以下三部分：1、氨基酸修饰的三明治型混杂卟啉酞菁稀土双层配合物的合成及光谱性质研究在自然界,卟啉化合物构成了血红蛋白、细胞色素及叶绿素等生物大分子的活性中心,参与生物体系的一系列重要过程。利用卟啉独特的结构和性能进行功能分子的设计、合成及应用研究一直受到化学、生物、医学各界的广泛关注。此前,科研工作者已合成了一系列的卟啉衍生物,试图模拟其生理特性,但到目前为止,还只是局限于相对简单的卟啉衍生物,且大都有很强的疏水性,无法模拟生物体内的真实环境。利用氨基酸对卟啉环进行修饰,能获得结构和性能更加接近天然卟啉的化合物。另外,由于氨基酸是蛋白质的重要组成部分,氨基酸侧链的引入使得整个卟啉分子对特定的蛋白质分子表现出选择性识别。据作者所知,目前仅有过氨基酸修饰的单层卟啉(或酞菁)金属配合物的报道,而相应的氨基酸修饰的三明治型双层(或三层)金属配合物的研究还未见报道。在本文中作者合成、分离和表征了三明治型混杂卟啉酞菁稀土双层配合物[EuⅢH{Pc(α-3-OC5H11)4}{TriBPP(NHR)}](R=H, C8H17)(1,2)[HoⅢH{Pc(α-3-OC5H11)4}{TriClPP(NHR)}](R=H,C8H17)(5,6)[HoⅢH{Pc(α-3-OC5H11)4}{TriBPP(NHR)}](R=H,C8H17)(9,10)和[HoⅢH{Pc(α-OC4H9)8}{TriBPP(NHR)}][(R=H,C8H17)(13,14),及其对应的N-(叔丁氧羰基)-L-苯基丙氨酸修饰的三明治型混杂卟啉酞菁稀土双层配合物[EuⅢH{Pc(α-3-OC5H11)4}{TriBPP(NR-L-Phe-Boc)}](R=H,C8H17)(3,4)[HoⅢH{Pc(α-3-OC5H11)4}{TriClPP(NR-L-Phe-Boc)}](R=H,C8H17)(7,8)[HoⅢH{Pc(α-3-OC5H11)4}{TriBPP(NR-L-Phe-Boc)}](R=H,C8H17)(11,12)和[HoⅢH{Pc(α-OC4H9)8}{TriBPP(NR-L-Phe-Boc)}](R=H,C8H17)(15,16)。通过质谱、元素分析、核磁共振氢谱和紫外可见吸收光谱等手段表征了手性氨基酸基团修饰的三明治型配合物的结构。2、具有C4对称性的手性三明治型混杂卟啉酞菁稀土双层配合物的合成、拆分及绝对构型的指认研究三明治型卟啉酞菁金属配合物具有独特的结构、性质和其在材料科学方面的应用潜力,人们已经对其开展了大量的研究工作。设计和制备新型手性三明治型混杂卟啉酞菁稀土配合物是开发其在材料科学和生命科学领域应用的重要基础。然而据作者所知,手性三明治型四毗咯金属配合物仍然少有报道。作者合成手性三明治型四吡咯配合物的策略是利用1,8,15,22-四(烷氧基)取代酞菁的C4h对称性。这一酞菁配体呈现单向旋转的取代基排列模式,从而具有一个前手性面。在该酞菁环的轴向两侧或任意一侧引入不同的结构单元后,通过大环的对称面不复存在,分子的对称性会降低到C4,甚至C2或C1,从而具有手性。通过这种思路,作者设计合成了具有C4对称性的手性混杂卟啉酞菁稀土三明治型双层配合物[HMⅢ{Pc(α-3-OC5H11)4}{TOAPP}][M=Y(1),Ho(2)；Pc(α-3-OC5H11)4=1,8,15,22-四(3-戊氧基)酞菁；TOAPP=meso-四(4-辛胺基苯基)卟啉],并通过了质谱、元素分析、核磁共振氢谱和紫外可见光谱等表征。利用X射线单晶衍射分析可以确定这些分子属于三斜晶系,在每个晶胞中包含有一对互为对映异构体的配合物分子,证明这两个配合物都是以外消旋混合物的形式存在。利用N-(叔丁氧羰基)-L-苯基丙氨酸(Boc-L-Phe-OH)作为手性拆分试剂,与配合物相结合形成非对映异构体,第一次成功的运用手性高效液相色谱技术对其进行了光学拆分。通过对实验所得的CD光谱数据与应用含时密度泛函理论方法模拟所得的CD光谱数据相比较,指认了该C4手性配合物的绝对构型。这一工作对于光学拆分具有相似手性源模式的化合物具有开创性的指导意义。3、新型萘基取代手性卟啉的合成及拆分研究由于光学活性的四吡咯大环衍生物和许多生物过程相关,并且具有多方面的应用潜力,因而激起了学者们极大的研究热情,目前已发现细胞色素P450能选择性地催化一系列的羟基化和环氧化反应,金属卟啉的手性催化引起了化学家们极大的兴趣,其中最主要的挑战是手性催化剂的合成。对于meso位取代的萘基卟啉,由于萘基9号位上的H原子与卟啉环的β位的H原子存在空间位阻,卟啉环上meso-取代萘基沿着C(meso)-C(nph)键的转动受到限制,只能在卟啉环一侧进行扰动。利用这一特性,作者设计合成了两种新型的meso位萘基取代的手性卟啉配合物：10-苯基-15-萘基-20-(4-十六烷氧基苯基)锌卟啉ZnPor(Ph)(Nph)(PhOC16H33)(1)和5-苯基-10,20-二萘基-15-(4-羟基苯基)锌卟啉ZnPor(Ph)(dNph)(PhOH)(2),并通过了质谱、核磁共振氢谱和紫外可见光谱等手段进行了表征。尝试使用手性高效液相色谱技术对其进行光学拆分,但是目前还未能达到拆分目的。合成新型手性卟啉并对其进行光学拆分进而研究其不对称催化性能将是未来工作的重点。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 intramolecular-interactions 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.Chiral porphyrinic compounds are abundant in living systems. Due to their fundamental importance in many biological processes, chiral porphyrins (Pors) have been extensively studied in view of biomimetic synthetic models over the past few decades. The phthalocyanine counterparts have only been reported recently. Our research work has been focused on the synthesis, characterization and resolution of chiral macrocyclic tetrapyrrole compounds include the following three parts:1. Amino Acid Modified Mixed (Porphyrinato) (Phthalocyaninato) Rare Earth Double-Decker Complexes:Synthesis and spectroscopic studiesPorphyrins play essential roles in hemoglobin, cytochrome, chlorophyll and other biological macromolecules and participate in the process of a series of important biological systems. Studies of molecular design, synthesis and application using the unique structure and properties features of porphyrin has been subject to chemical, biological, and medical scientists. Previously, researchers have synthesized a series of porphyrin derivatives, trying to simulate the physiological characteristics, so far, it is still limited to relatively simple derivatives, which have very strong hydrophobicity.. The use of amino acids on the porphyrin ring was modified to be closer to the natural structure and properties of porphyrin compounds. Amino acid is the major component of proteins; the introduction of amino acid side chain makes the whole porphyrin molecule to specific protein molecules demonstrating selective recognition. According to our knowledge, only few studies on monomeric porphyrin (or phthalocyanine) complexes modified by amino acid have been reported. We have prepared a new series of sandwich type mixed (porphyrinato) (phthalocyaninato) rare earth double-decker complexes [EuⅢH{Pc(α-3-OC5H(11))4}{TriBPP(NHR)}] (R= H, C8H(17)) (1,2), [HoⅢH{Pc(α-3-OC5H(11))4}{TriCIPP(NHR)}] (R= H, C8H(17)) (5,6), [HoⅢH{Pc(α-3-OC5H(11))4}{TriBPP(NHR)}] (R= H, C8H(17)) (9,10) [HoⅢH{Pc(α-OC4H9)8}{TriBPP(NHR)}] (R-H, C8H(17)) (13,14) and the corresponding amino acid modified double-deckers [EuⅢH{Pc(αa-3-OC5H(11))4}{TriBPP(NR-L-Phe-Boc)}] (R= H, C8H(17)) (3,4), [HoⅢH{Pc(α-3-OC5H(11))4}{TriClPP(NR-L-Phe-Boc)}] (R= H, C8H(17)) (7,8), [HoⅢH{Pc(α-3-OC5H(11))4}{TriBPP(NR-L-Phe-Boc)}] (R-H, C8H(17)) (11,12) [HoⅢH{Pc(α-OC4H9)8}{TriBPP(NR-L-Phe-Boc)}] (R= H, C8H(17)) (15,16) for the first time. These complexes have been fully characterized by elemental analyses and a wide range of spectroscopic methods, including Mass, UV-Vis and NMR.2. Mixed (Phthalocyaninato)(Porphyrinato) Rare Earth Double-Decker Complexes with C4-Chirality:Synthesis, Optical Resolution, and Absolute Configuration AssignmentWe are motivated to design and prepare new chiral sandwich-type phthalocyaninato and porphyrinato rare earth complexes with a view to creating novel applications in material science and catalysis. The strategy towards chiral sandwich-type tetrapyrrole rare earth complexes involves utilization of 1,8,15,22-tetrakis(alkoxy)-substituted phthalcoyanine ligand with C(4h) symmetry. This tetrapyrrole ligand possesses a single-handed rotational arrangement of the substituted pattern, actually two enantiotopic faces. As a result, attachment of the entity on either side of the Pc ring will eliminate the mirror plane of C(4h) symmetry and lead to chiral molecules with a C4 or even further decreased symmetry, C2 or C5. In the present chapter, we describe the synthesis and first optical resolution of mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes [HMⅢ{Pc(α-3-OC5H(11))4}{TOAPP}] [M= Y (1), Ho (2)] with C4 symmetry, by using a chiral HPLC technique combined with the formation of their diastereotopic mixture, utilizing L-Boc-Phe-OH as the chiral resolving agent. The absolute configurations of these C4-chiral complexes were assigned by comparing experimental CD spectra with simulated one on the basis of time-dependent density functional theory.3. Synthesis and Optical Resolution of Naphthalene-Substituted Chiral PorphyrinThere has been a growing interest in optically active tetrapyrrole derivatives because of their biological relevance and various potential applications. Chiral porphyrins, ranging from synthetic to naturally occurring analogues, have been extensively studied over the past few decades. A series of hydroxylation and epoxidation selectively catalyzed by cytochrome P450 has been reported recently. Catalysts of chiral metalloporphyrin have attracted great interest in chemists, and the most important challenge is the synthesis of chiral catalysts. For the meso-substituted naphthyl porphyrin, rotation of the naphthyl along the C (meso)-C (nph) bond is restricted only in one side of the porphyrin ring and perturbed due to the steric hindrance. We have prepared two novel meso-naphthyl substituted chiral porphyrins: ZnPor(Ph)(Nph)(PhOC(16)H(33)) (1) and ZnPor(Ph)(dNph)(PhOH) (2), which have been characterized by Mass, UV-Vis and NMR. Resolution of the two complexes using a chiral HPLC technique has been failed. Synthesis and optical resolution of novel chiral porphyrins, study of their performance as asymmetric catalysis will be the focus of future work.更多还原