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The Synthesis of Tetraphenylethylene and Calixarene Derivatives Based on Molecular Recognition

Author: XieDeXun
Tutor: AnDeLie
School: Hunan University
Course: Organic Chemistry
Keywords: Tetraphenylethylene Aggregation Induced Emission(AIE) CalixareneSelf-Assembled Monolayers(SAMs) Suzuki Reaction SonogashiraReaction
CLC: O621.3
Type: PhD thesis
Year: 2013
Downloads: 155
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Abstract


The research of this particle is mainly made up of two parts. In the first part, a series oftetraphenylethylene derivatives with the property of aggregation induced emission(AIE) weredesigned and synthesized, and their properties were studied. The second part showed thedesign and synthesis of some calixarene and thiacalixarene derivatives with molecularrecognition. The details are shown below:1. Some tetraphenylethylene derivatives with active recognizing groups and asalicylaldehyde azine with the ability of ion recognition were designed and synthesized, basedon the AIE properties. In order to study the recognition effects of metal ion of thesecompounds, Tetraphenylethylene derivative5and salicylaldehyde azine9were applied to thedetection of metal ion, and the results were satisfying. In our research, Compound5showedhigh selectivity in the recognition of Al3+. The dynamic light scattering(DLS) and SEMdetection confirmed that a polymerized state of Compound5was formed. On the other hand,the salicylaldehyde azine9showed high selectivity in the recognition of Zn2+, and DLS andSEM detection also confirmed its polymerization2. Based on our previous research, a novel series of cone-shaped calixarene andthiacalixarene derivatives of different sizes and sulfide side-chain amounts were designed andsynthesized, in which calixarenes and thiacalixarenes were used as ligands. Since the structureof calixarenes could be easily modified, we chose4-iodobenzyl bromide for the selectivemodification to the phenol hydroxyl group at their bottom. A series of double, triple andtetra-substituted calixarene intermediates with aryl halide side-chains were prepared withdifferent bases used as catalysts, such as sodium carbonate, sodium hydride, cesium carbonateand potassium tert-butoxide. The calixarene derivatives with sulfide function groups wereprapared from the intermediates with different terminal block molecules via Suzuki couplingreaction or Sonogashira reaction. The structures of all target compounds were confirmedthrough IR, NMR and MS. Moreover, the structure of compound33, one of the thiacalixarenederivatives, was examined by X-ray crystallography. These compounds will be applied in theself-assembled nano-gold monolayers research and their behavior will be observed. We hopeto learn more about the influence of the ligand molecules to the physical and chemicalproperties of modified gold nanoparticles.3. Since calixcrowns have been playing an important role in areas like ion extraction andchemical sensoring, we chose them as our research objects and designed a series of calixcrown derivatives with different cavity sizes. The intermediates containing halogenatedalkane were successfully prepared via Williamson reaction, and target compounds wereprepared by reaction of the intermediates with sodium sulfide or sodium polysulfide. Thestructure of target compounds were confirmed via XRD, showing that the products werecalixcrown derivatives, not the dicalixarene derivatives.4. Functional molecules with multi-thiol or methylsulfide groups were usually applied asligands in the self assembly of gold nanoclusters. Delighful results were achieved in ourprevious research in this area, and this time we chose1,3-alternate conformer thiacalixarenederivatives as the research object. A series of novel thiacalix[4]arene ligands were designedand synthesized, and they were supposed to be of special value in gold nanoclusters research.The intermediate1,3-alternate conformer thiacalixarene derivatives were preparedsuccessfully with cesium carbonate used as catalyst. The intermediates with aryl halideside-chains were dealt with terminal block molecules via Suzuki coupling reaction orSonogashira reaction, giving the target thiacalixarene derivatives of different sizes. Thestructures of target compounds were confirmed through IR, NMR and MS. Moreover,compound47b was examined by X-ray crystallography, the result proved that our supposedstructure was correct. These thiacalixarene derivatives will be applied in the gold clustersresearch as a new type of ligands.

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