Preparation And Stucture Investigation Of Hydrogen-Bonding Induced Carboxylic Acid-Amine Complex

It is one of the interesting research topics in supramolecular chemistry to design and synthesize novel hydrogen-bonding supramoleculars. Because of the stability, direction, and saturation of hydrogen bond, hydrogen bond interactions in materials science and life science attract much attention. Hydrogen bond is essential in determining the complex character and designing new complex. Eight carboxylic acids and two amines were designed and synthesized in this thesis. And four hydrogen-bonding self-assembly complexes were synthesized and their crystal structures were also studied. Specifically, the content in this thesis is listed below:1. We have successfully synthesized new amino acetic acid compounds (2,4-difluorophenyl)amino acetic acid (1), (2,4-difluorophenyl)azanediyl diacetic acid (2), (2,5-difluorophenyl)amino acetic acid (3), (2,4,6-trifluorophenyl)azanediyl diacetic acid (4) and new benzimidazole-carboxylic acid compounds 11-oxo-11H-benzo[4,5]imidazo[2, 1-α]isoindole-8-carboxylic acid (5a), 11-oxo-11H-benzo[4,5]imidazo[2, 1-α]isoindole-7-carboxylic acid (5b),7-oxo-7H-benzo[de]benzo[4, 5]imidazo[2,1-α]isoquinoline-10-carboxylic acid (6a),7-oxo-7H-benzo[de] benzo[4,5]imidazo[2,1-α]isoquinoline-11-carboxylic acid (6b). These compounds have not been reported.2. By solvent slow evaporation in acetone system we obtained single crystal of hydrogen-bonding complex [F-C6H4-NH=C(CH3)2]+ [(COOH)3C6H2COO]- (Ⅰ), which was belong to monoclinic system, space group Cc, with cell parameters:a=1.0378(4) nm,b=1.6213(6) nm, c=1.1259(4) nm,β=103.898(5)°, V= 1.8390(12) nm3, Z=5. Complex I has potential non-linear optical property.3. By solvent slow evaporation in DMF/EtOH mixed system we obtained single crystal of hydrogen-bonding complex [F-C6H4-NH3]+ [(COOH)3C6H2COO]- (Ⅱ), which was belong to monoclinic system, space group Cc, with cell parameters:a=0.9801(4) nm,b=1.9127(6) nm, c=0.7963(4) nm, V=1.4602(12) nm3, Z=4. In acetone system, we obtained single crystals of hydrogen-bonding complex [C6H2F3N-(CH2COOH)2] (Ⅲ) and hydrogen-bonding complex [CF3-C6H4-NH3]+[F2-C6H3N(CH2)2COOHCOO]-(Ⅳ). ComplexⅢis in monoclinic and Cc space group. Cell parameters:α=15.171(4) nm,b=9.201(6) nm, c=8.462 (4) nm, V=1.0987(12) nm3, Z=4. Complex IV is in monoclinic and P-1 space group. Cell parameters:α=5.3370(5) nm,b=10.9880(6) nm, c=15.3270(6) nm, V=0.87032(10) nm3, Z=2.4. By hydrogen-bonding, crystal structure of complex I is a two-dimensional infinite layered structure. The crystal structure of complexⅡis a pyromellitic acid anion reticular structure filled with 4-fluoroaniline cation. The crystal structure of complexⅢis a two-dimensional infinite layered structure. And the crystal structure of complexⅣis a three-dimensional stair-like structure.