Reassembly Self-Sorting Behavior And Studies On Hierarchical Assembly, Molecular Catalysis & Recognition Based On Glycoluril Derivatives

Biological systems offer exquisite examples of the way in which spatially and temporally controlled intermolecular noncovalent forces can lead biomolecules (e.g. phospholipid, polypeptide, nucleic acid, and antibody) to the creation of higher order biological function structures (e.g. biomenbrane, protein, DNA/RNA, oligose, and ion channel) and molecular behaviors (e.g. heterR-Dssemblies Rf bDsic pDirs Rf DNA’s self-replication). fnspired by Nature, the study on molecular behaviors is one of the most important topics in supramolecular chemistry. Meanwhile, molecular behaviors with selectivity are extensive potential for applications in polymer or surface mDteriDis, Dnd Ds DmRlecule-level "prRgrDmming lDaguDge"in mRleculD(?) mrDchine.fn supramolecular chemistry, molecules have exhibited a variety of molecular behaviors in the processes of recognition and assembly, mainly including self-assembly, self-organization, self-recognition, self-discrimination, self-replication, self-growth, self-coiled, self-catalysis, self-complementary, and self-sorting. This dissertation systematically study on molecular self-sorting in supramolecular chemistry, and design and synthesize a sophisticated system of reassembly self-sorting which is a high level system of self-sorting between two heterodimers formed through tWR independent reDssembled prRcesses, nDmed it Ds D new term "reDsembly self-sRrting". pubsequently, the rule of self-sorting is used in contracting highly hierarchical Dssemblies——nRncRvDlent mDrcRcycle with nRncRvDlent mDrcRcycle nDaRtube Dnd bilDyer netwRrN; in addition, glycoluril skeleton as building blocks also is used for the applications in organic catalysis and molecular recognition.Chapter Nmainly focus on the preparation and application of supramolecular self-sorting systems. t e attempt to outline a full view of self-sorting in science, including fN in classical supramolecular chemistry, self-sorting in the processes of self-assembly for constructing exquisite structures, or exclusive host-guest recognitions; 2) the applications of molecular self-sorting in material science, nanotechnology, dynamic combinatorial chemistry, and classical organic synthesis.Chapter 2 describe that the reassembly and self-sorting of dimeric molecular clipsⅡ-1-Ⅱ-14. t e successfully prepare two highly selective heterodimer systems:heterodimer 1-4 (x1-4= 92.3%) and heterodimer 8-11 (x8-11= 92.N%) in C6D5CD3/CDCl3, respectively. fnterestingly, two heterodimers are capable of maintaining perfectly self-sorted assembles in this four-component system. This NNNN mixtures of 1,4, (①)-8 Dnd (①)-11 is a high level system of self-sorting between two heterodimers formed through two independent reassembled processes, nDmed it Ds D new term "reDssembly self-sorting".fn chapter 3, we first propose the strategy of self-sorting hierarchical assembly for constructing complicated and high-level structures based on the principles of self-sorting from chapter 2. t e have crystallographically characterized an intriguing non-covalent macrocycle within non-covalent macrocycle complex comprising an interior (Mel e)12 cyclododecamer within an exterior ((+)-1-(-)-1)6 molecular clip cyclododecamer. The interior cyclododecameric Mel e assumes a crown-like geometry that has not been predicted theoretically or observed experimentally.fn chapter 4, we design and synthesize a series of molecular clips ligandsⅣ-1-Ⅳ-2 with potential abilities of dimeric assembly to gain a dimer and metal-coordination. t e use molecular clip ligandsⅣ-1-Ⅳ-2 as building blocks to prepare the novel metal-organic frameworks formed from dimeric molecular clipsⅣ-1·Ⅳ-1 orⅣ-2·Ⅳ-2. These metal-organic frameworks are characterized by1e NMo, X-ray, ESf-MS, and fluorescence experiments. t e believe that these metal-organic frameworks with cell-like cavities will be the potential value for applications in molecular recognition, catalytic reactions, gas absorption, fluorescent sensing, and optoelectronic materials.fn chapter 5, we develop a way for the first time to use thioglycoluril as a novel hydrogen-bonding organocatalyst in combination with NBS for a-monobromination of 1,3-dicarbonyl compounds. Based on the analysis for the crystal structure of thioglycoluirl, we speculated that a key step in the mechanism may include the promotion of enolate formation and the activation of NBS. t e believe that thioglycoluril and its derivatives will be extensively applied in organic catalysis, even chiral catalysis.fn chapter 6, we synthesize five molecular clipsⅥ-1-Ⅵ-5 with two cis-thiourea groups as potential e-bonded binding sites to anions. By r s-vis,1e and 19F NMo experiments, we observe that molecular clipⅥ-1 exhibits a.highly selective affinity to fluoride ion. This study first uses the skeleton of glycoluril molecular clip acts as an effective template with an appropriate distance of separation between the thiourea groups to sense fluoride ion.fn conclusion, this dissertation achieves a series of periodical results in the area of supramolecular self-sorting. Based on macro-and micro-phenomenon of self-sorting, the studies of dissertation contain the observation of molecular self-sorting behaviors, hierarchical assembly of assembled nanotube and frameworks, and e-bonded catalysis and molecular recognition.