【作者】 曹晶晶；

【导师】 田禾； 马骧；

【作者基本信息】 华东理工大学 ， 应用化学， 2014， 博士

【摘要】 分子机器是超分子化学领域最具挑战的研究热点之一。迄今为止,科学家们报道了大量结构独特、功能新颖的分子机器体系,并且在诸多领域显示出广阔的应用价值。人造分子机器在外界刺激下,也可以像宏观机器一样发生运动,并且这种运动可以被检测到。传统上,分子机器的位置状态可以通过紫外-可见吸收光谱法、荧光光谱法、核磁共振波谱法、循环伏安法以及圆二色波谱法等手段进行检测和识别。同荧光一样,磷光也是光致发光的一种,并且具有发射波长和寿命更长、信噪比更高、更易于检测等优点。因此磷光特别是室温磷光也可以用于检测和识别分子机器的位置状态。本论文一方面利用金属卟啉的室温磷光性能,合成了具有室温磷光响应的酸碱可控的双稳态分子梭,另一方面利用环糊精诱导室温磷光,构建了具有室温磷光输出的INHIBIT逻辑门。从而使得室温磷光成为检测和识别分子机器的一种新手段,为构建多模式的分子机器提供了些新的思路和方法。具体内容概括如下：第一章内容中,我们简单阐述了分子机器的研究进展。首先介绍了分子机器的定义和分子机器的三种主要的类型,即轮烷、类轮烷和索烃；其次举例介绍了分子机器的几种主要的能量驱动方式：化学能、电化学能、光化学能等；再次举例介绍了分子机器运动状态的表征方法,包括紫外-可见吸收光谱法、荧光光谱法、核磁共振波谱法、循环伏安法以及圆二色波谱法等,并对室温磷光光谱法这种新的表征方法进行了简要阐述；最后对分子机器在分子逻辑门、纳米级分子阀门、超分子聚合物以及超分子凝胶等领域的潜在应用作了举例说明。第二章内容中,我们设计和合成了一类由非金属或金属锌卟啉修饰的冠醚化合物和不同客体分子自组装形成的类轮烷体系,并通过核磁共振波谱、质谱、紫外-可见吸收光谱和荧光光谱等方法对其进行了结构表征和性能研究,确认了主客体之间的结合比例和结合常数。第三章内容中,我们在上一个工作的基础上,设计合成了一类酸碱调控的双稳态分子梭R1、R2和R3,其中轮烷分子R3的运动位置状态可以通过室温磷光光谱法来检测和识别。通过核磁共振波谱、质谱、紫外-可见吸收光谱、荧光光谱,特别是室温磷光光谱等对这些轮烷分子进行了结构表征和性能研究。第四章内容中,我们分别构建了基于光控分子梭的二元和三元体系,通过一维和二维核磁共振氢谱、圆二色光谱、紫外-可见吸收光谱以及室温磷光光谱等对其进行了结构表征和光照前后的性能研究。基于二元体系在光照前后的圆二色信号和室温磷光信号的变化,构建了多个INHIBIT逻辑门。第五章内容中,我们合成了具有萘和溴萘基团的卟啉化合物并与葫芦脲形成超分子聚合物,对这种聚合物进行了结构表征和性能测试。在已制备的螺吡喃单分子层覆盖的金纳米棒及金纳米颗粒基础上,通过紫外-可见吸收光谱、红外光谱、透射电镜以及拉曼光谱等进行了形貌表征和性能研究。第六章内容中,对本论文进行了总结。更多还原

【Abstract】 Molecular machines, as one of the most challenging topic in the field of supramolecular chemistry, have attracted continuing interest and attention. A variety of appealing examples in this field have been fabricated over the recent years, with applications in many areas. Component of the artificial molecular machines could also have relative movement under external specific stimuli as the macro machines, and the movement can be detected. The output signals of most molecular machines were observed by NMR, cyclic voltammetry, circular dichroism, and UV-vis absorption or fluorescence emission. Phosphorescence, especially the room temperature phosphorescence (RTP), is another excellent method expected to be used in this field. RTP can not merely respond quickly and be detected with low cost, but has more advantages, such as longer emission wavelengths and lifetimes, larger Stokes’shifts, higher signal-to-noise ratios, easily measurable lifetimes, etc.In this dissertation, we designed and constructed some pH-controlled bisable molecular shuttles with room temperature phosphorescence on the base of the metalloporphyrin. On the other hand, we constructed a INHIBIT logic gate with room temperature phosphorescence output making use of the Cyclodextrin induced room temperature phosphorescence (CD-RTP). Thus it provides a new means for detecting and identifying molecular machines and for the construction of complicated multi-mode molecular machines. A brief summary is given as follows:Chapter I:We mainly expound the research progress of molecular machine in recent years. The definition and three species of molecular machine, namely rotaxane, pseudorotaxane, and catenane were elaborated. Driving forces of switchable molecular machine, like chemical energy, electrochemical energy, light energy, and others, were exemplified. The identifications of movement of molecular machine, like NMR spectra, ultraviolet-visible absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, circular dichroism spectra were introduced, and room temperature phosphorescence spectroscopy as a new method was specially stated. In addition, the potential application of molecular machine in such areas as molecular logic gate, molecular nanovalve, supramolecular polymer and organic gel were also illustrated.Chapter Ⅱ:We designed and synthesized a series of novel24-crown-8ether connected with free-base or metal complexed porphyrin moiety covalently by template method, and characterized by standard spectroscopic methods. The association constant between the host and the guest was determined by fluorescence titration experiment.Chapter Ⅲ:We designed and synthesized a series of novel pH-controlled distable molecular shuttles R1-R3, comprised of metalloporphyrin-based dibenzo[24]crown-8macroring and anthracene unit as one stopper by click chemistry, and the motion of R3could be read out by RTP signals.Chapter Ⅳ:We prepared a light-driven [1]Pseudorotaxane based on the self-inclusion complexation of an azobenzene-modified β-CD, and its photoisomerization and their complexation behaviors with a-bromonaphthalene were adressesed by ICD and room temperature phosphorescence. The INHIBIT logic gates were fabricated conveniently in aqueous solution, utilizing RTP or ICD as outuput.Chapter Ⅴ:We synthesized two compounds which contains tetrapyridylporphyrin core connected with naphthalene or bromonaphthalene and obtained their supramolecular polymer based on the host-guest interaction between CB[7]/CB[8]. We characterized spiropyran coated gold nano rods (GNR) and gold nano particles (GNP) by ultraviolet absorption spectra, fluorescence emission spectrum, IR spetra and Raman spectra. The photochromic properties of spiropyran can affect the plasmon peaks of GNRs but not GNPs.Chapter Ⅵ:A summary of the contents of the entire dissertation更多还原