【作者】 邓艳华；

【导师】 马长勤；

【作者基本信息】 山东大学 ， 无机化学， 2011， 硕士

【摘要】 手性是自然界与生命休戚相关的基本属性之一。在生命体系中的大部分基本单元都是手性分子,许多生物化学现象的本质即为手性识别,因此在研究生物体内各种生物现象时,从分子水平上来模拟生物功能则具有至关重要的意义。由于在分子电子学、分子信息存储、非线性光学及材料学等领域,作为新型的功能材料的卟啉酞菁化合物以及三明治型稀土卟啉酞菁配合物拥有广阔的应用前景,因此对于分子手性和超分子手性的表达、传递、存储及调节的研究具有重要的科研和研究价值。尽管通过引入手性信息研究者们得到了带有手性的卟啉酞菁类化合物,但使其在卟啉、酞菁分子及超分子水平上顺利表达出来并将其组装制造出最终希望得到的高级有序的手性纳米结构,这对研究者而言仍是一个挑战。到目前为止,对手性酞菁及手性卟啉酞菁混合双层的报道还比较少。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手性酞菁及手性卟啉酞菁混杂双层配合物,研究在分子水平及超分子水平上手性酞菁及稀土三明治配合物手性信息的传递和表达,分析了分子水平及超分子水平上手性信息的传递和表达与分子结构的关系,为合成新颖的手性卟啉酞菁化合物及其衍生物提供了重要路线和机理。主要内容包括：1、光学活性手性酞菁的合成及其组装纳米结构研究由于具有光学活性的手性四吡咯大环衍生物和许多生物过程有关,激起了许多研究者的兴趣,人们通过各种方法合成了大量具有特定性质的手性化合物,并通过氢键、π-π堆积作用、配位键、静电作用以及范德华力等非共价键作用将这些手性化合物组装成了超分子,研究了手性信息在分子水平及超分子水平上的传递与表达,同时研究了非共价键在手性信息传递及表达过程中的作用。本章中,我们以带有手性基团的配体在催化剂DBU和醋酸锌的存在下,合成了(S)-构型的手性锌酞菁(compound 1),使用溶剂扩散法组装得到有机纳米聚集体,并通过紫外(UV)、圆二色(CD)、透射电镜(TEM)、扫描电镜(SEM)、X射线光电子能谱(XPS)等表征手段,研究了该锌酞菁的组装性质,研究表明Zn-Ocrown ether配位键的存在对聚集体的形貌存在较大影响。化合物锌酞菁在手性取代基的影响下,通过π-π键、Zn-Ocrown ether等作用力聚集形成了长约数十μm,宽约2.1μm,螺距约为4.5μm的一维的螺旋纳米带状结构；研究结果表明,在调节、控制酞菁分子自组装纳米结构中,手性基团的诱导效应和非共价键尤其是π-π堆积、金属配位键的协同作用起着非常重要的作用,特别是金属配位键对纳米结构的形貌、维度、手性及螺距大小的影响不容忽视。其结论会为我们了解手性信息在超分子水平上的传递、表达及通过分子设计来制备、调控有机纳米功能材料提供非常有用的信息。2、手性三明治型卟啉酞菁配合物的设计、合成及光谱学性质的研究三明治型卟啉酞菁金属化合物一直以来都是化学、物理和材料工作者的研究重点,具有共轭π电子结构的该类化合物在非线性光学、液晶、导电、超导、磁性、光电转换等方面扮演着特殊和关键的角色,其研究对于发现新型光学、电学和磁学性能,研制新型光、电和信息功能材料以及抢占该领域在生产技术和应用研究方面的制高点都有着重大和深远的意义。但是,迄今为止,手性三明治型卟啉酞菁金属化合物研究的还很少。在本章中,我们以带有手性基团的手性配体在金属锂存在下,合成了手性自由酞菁,然后再与制备的H2TC1PP在乙酰丙酮铕盐的存在下得到Eu (TCIPP) [Pc(α-2-OC8H17)4]和EuH (TCIPP) [Pc(a-2-OC8H17)4],并对二者的性质进行了相关的表征,包括氢谱、质谱、紫外、圆二色谱,着重研究了手性信息的传递与表达。研究表明,手性信号由酞菁环的周边位置顺利传递到卟啉酞菁混杂双层上,非质子化卟啉酞菁混杂双层和质子化卟啉酞菁混杂双层均具有手性信号,但由于Eu(TCIPP) [Pc(α-2-OC8H17)4]和EuH(TCIPP) [Pc(α-2-OC8H17)4]在分子结构上的差别(研究证明,质子化卟啉酞菁混杂双层中卟啉环上存在一个氢),非质子化卟啉酞菁混杂双层和质子化卟啉酞菁混杂双层在Soret带具有不同强弱的手性信号,体现出分子结构细微的差别即可导致手性信号的不同,这为卟啉酞菁混杂双层配合物在非线性功能材料的应用提供了可能。更多还原

【Abstract】 Chirality which is closely related with the nature of life is one of the basic attributes of nature. Chiral molecules are most basic unit in the life system. Owing to the unique optical, electrical, and properties, associated with the intriguing intramoleculaπ-πinteractions, porphyrins, phthalocyanines, as well as sandwich type rare complexs as a novel functional materials, have been expected to be widely potential application in materials science, such as molecular electronics, molecular information storage, and nonlinear optics, etc. Recently, to obtain ordered supramolecular aggregates and nano-scale assembly, besides the expression, transmission, storage and regulation of molecular/ supramolecular’s chirality, have attracted increasing attentions.It must be pointed out that self-assembly of functional molecules into a prerequisite nanostructure with desirable dimension and morphology via controlling inter-molecular interaction and the introduced chirality informations still remains a great challenge for scientists. In order to investigate supramolecular aggregation behaviors, supramolecular assembly methodology of chiral phthalocyninato complexs, the role of coordination bond in tuning the aggregates’s morphology and the expression of chiral information at molecular / supramolecular level, in this thesis several chiral phthalocyanine derivatives are designed and synthesized. Our research work has been focused on the following respects:1. Synthsis and Novel Helical Nano-structures of Optically Active Metal PhthalocyanineNovel optically active metal phthalocyanine (1) decorated with four butoxy chains linked to the phthalocyanine ring was designed and prepared. Helical Nano-structures Self-Assembled from Optically Active Phthalocyanine Derivatives Bearing Four Optically Active butoxy:Effect of Metal-ligand Coordination on the Morphology, Dimension, and Helical Pitch of Self-Assembled Nano-structures. Compound 1 was prepared from the tetramerization of corresponding phthalonitriles, S-3-(2’-methel butoxy) phthalonititrile, in the absence and presence of Zn (OAc)2-2H2O template, respectively, promoted by organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Their self-assembly behavior has been comparatively investigated by electronic absorption and circular dichroism (CD) spectroscopy, transmission electron microscope(TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) technique, and X-ray photoelectron spectroscopy (XPS). The metal phthalocyanine self-assembles into highly ordered fibrous nano-structures with right-handed helicity through the hierarchical manner via one-dimensional helices with chirality determined by the optically active butoxy side chains, revealing the effect of metal-ligand coordination bonding interaction on the morphology, dimension, handedness, and the helical pitch of self-assembled nano-structures.2. Mixed (Phthalocyaninato)(Porphyrinato) Rare Earth Double-Decker Complexes:Synthsis and spectroscopic studiesWe are motivated to design and prepare new chiral sandwich-type phthaiocyaninato and porphyrinato rare earth complexs with a view to creating novel applications in material science and catalysis. The strategy towards chiral sandwich-type tetraphyrrole rare earth complexes involves utilization of 1,8,15, 22-tetrakis (octyloxy)-substituted phthalcoyanine ligand. In the present chapter, we describe the synthesis and spectroscopic studies of mixed (phthalocyaninato) (porphyrinato) rare earth double-decker complexes [EuPc*(TClPP)] (compound1)] and [EuHPc*(TClPP)](compound2)][(Pc*=Pc(α-D-2-octyloxy)4). These two compounds were characterized by 1HNMR, MS and various spectroscopic methods including IR, UV-vis and CD. Their UV-vis and CD spectra are different. Both compounds display CD signal in the Soret absorption region of mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes, indicating effective chiral information transfer from the chiral peripheral substituents to compound chromophore at the molecular level. And the intensity of CD signal is different between the compound1 and compound2.更多还原