Structure Characterization And Research Of Self-Assembly Of Supramolecular Complexes With Hydroxy-Naphthoic Acid And N-Containing Heterocyclics

Supramolecular complexes have attracted extensive attention owing to their good molecular design and tailorability and potential utilization value in the fields of catalysis, magnetism, pharmacy, non-linear optics, etc. With the development of supramolecular chemistry, organic carboxylic acids, particularly aromatic carboxylic acids have been searched and reported in large volumes in the aspects of suramolecular self-assembly and coordination polymer for their diverse coordination patterns. Herein, four kinds of hydroxy-naphthoic acid are employed as main ligands to synthesize 20 novel supramolecular complexes with some typical N-containing heterocyclics by using slow evaporation method in room temperature. Then the cocrystalline products were characterized by single crystal X-ray diffraction, infrared, elemental analysis and thermogravimetric analysis, respectively. The thesis is divided into five chapters:In chapter one, we described briefly the basic conception, theory and research method of supramolecular chemistry. Then the research status and prospect on this theme were summarized.In chapter two, we employed 2-hydroxy-6-naphthoic acid as the main ligand, l,4-bis(2-methylimidazoly)butane (L1),1,4-bis(imidazol-1-yl-methyl)benzene (L2), 1-phenyl piperazine,2-amino-4-hydroxy-6-methyl pyrimidine,4,4’-bipyridine, 5,5’-dimethyl-2,2’-dipyridine,2-amino-4,6-dimethyl pyrimidine as the second ligand and used slow evaporation method in room temperature to synthesize seven novel multidimensional supramolecular complexes 1-7:(1) [(C10H16N42+)0.5·(C11H7O3-)](2) [(C14H18N42+)0.5·(C11H7O3-)](3) [(CioHi5N2+)·(C11H7O3-)·H2O](4) [(C5H8N3O+)·(C11H7O3-)·(C5H7N30)·H2O](5) [(C10H8N2)0.5·(C11H803)](6) [(C12H12N2)·(C11H8N3)·H2O](7)[(C6HioN3+)·(C11H703-)·(C11H803)·H20] We varied the stoichiometries of 2-hydroxy-6-naphthoic acid and N-containing heterocycles, solvents and the proportion of mixed solution to make the supramolecular structures diversiform. Then we characterized the structure and discussed the effect of various non-covalent bonds and typical supramolecular synthons for their structures.In chapter three, we selected 2-hydroxy-3-naphthoic acid as the main ligand and 3-hydroxy pyridine,2-amino-4,6-dimethoxy pyrimidine,2-amino-4,6-dimethyl pyrimidine,1-phenyl piperazine, cyclohexylamine, dicyclohexylamine, 1,10-phenanthroline as the N-containing building blocks to prepare seven new supramolecular complexes 8-14 under same conditions:(8) [(C5H6NO+)·(C11H7O3-)](9) [(C6H10N3O2+)·(C11iH7O3-)](10) [(C6HioN3+)·(C11H703-)](11)[(C10H15N2+)·(C11H7O3-)](12) [(C6H14N+)·(C11H7O3-)](13) [(C2H24N+)·(C11H7O3-)](14)[(C12H9N2+)·(C11H7O3-)·(C11H8O3)] We determined their crystal structures utilizing X-ray diffraction techniques, and further investigated their physicochemical property by elemental analysis, IR spectroscopy, TGA. The analysis of weak interactions, including hydrogen bonds and aromatic stacking interactions, and primary hydrogen-bonded synthons in the crystals of 2-hydroxy-3-naphthoic acid with various N-containing cocrystal formers (coformers) is presented.In chapter four, 1-hydroxy-2-naphthoic acid were employed as acid-containing ligand to crystallize with tetramethylpyrazine,1,10-phenanthroline, and L2, affording three novel 3D supramolecular co-crystals 15-17:(15)[(C8H12N2)0.5·(C11HO3)](16)[(C12H9N2+)·(C11H7O3-)·(C11H8O3)](17) [(C14H14N4)0.5·(C11H8O3)] Their crystal structures were determined and analysed by single X-ray diffraction. And we further studied the influence of different non-covalent bonds for structures of the co-crystals.In chapter five,2-hydroxy-l-naphthoic acid ligand was applied to crystallize with 2-amino-4-hydroxy-6-methyl pyrimidine,2-amino-4,6-dimethyl pyrimidine and L1 under general conditions, affording three new 3D supramolecular salts 18-20:(18) [(C5H8N3O+)·(C11H7O-)·(C5H7N3O)·H2O](19)[(C6H10N3+)·(C11H7O3-)](20)[(C10H16N42+)0.5·(C11H7O3-)]Single crystal X-ray diffraction studies show that total proton transfer from acid to coformer occurs in compounds 1-4,8-13,18-20, partial proton transfer occurs in 7, 14,16, and no proton transfer in 5-6,15 and 17. All organic crystals exhibit 3D supramolecular networks, except for 5,11 and 13. In these complexes, the carboxylic acid ligands and N-containing ligands interact each other via large numbers of hydrogen bonds, making the supramolecular structures more stable and diversiform.