Study On Supra-molecular Interaction In Crystal Structure Of Compounds With Phenanthroline And Multiple-substituted Benzoate As Ligands

Modern chemistry has realized that two or more chemical species could be held together by intermolecular interactions into orderly structure with special properties and functions. Supra-molecular chemistry includes the study of intermolecular interaction and molecular self-assemble. The non-covalent intermolecular interactions, such as hydrogen bonding, hydro-phoblic interaction,Ï€-Ï€interaction, etc., are called supra-molecular interaction. The cooperation between supra-molecular interactions forms strong force with direction and strength which effectively to construct functionalized supra-molecular structure.Studying on the nature of supra-molecular interaction and mastering the rule of molecular self-assemble are crucial to design and develop new materials with optical or electro-properties and biological-functional materials. This paper studies on intermolecular interactions, especially aromatic stacking interaction. Based on Hunter-Sanders' model, we observed the influence of multiple substituted group on benzene ring toward aromatic interaction in order to seek the nature of aromatic stacking interaction.In this paper, 5 unreported complexes (â… )-(â…¤) were synthesized in our lab, with 1,10-phenanthlorine as neutral ligand, 2,4-dihydroxybenzoate, 2,6-dihydroxybenzoate and 4-chlorosalicylate as anion ligands, and Zn^â…¡,Mn^â…¡,Sr^â…¡as center metal ions:(â…£), [Zn(â…¡)(C₇H₄ClO₃)₂(C₁₂H₈N₂)(H₂O)] (V), their three-dimensional structures were determined by single X-ray diffraction method. Useful information about aromatic stacking interaction and their supra-molecular structures was obtained.Studying the behavior of different multiple-substituted benzoate ligands involved in aromatic stacking, we found that: aromatic stacking interaction existed between 4-chlorosalicylate ligands in (â…¤). In related literatures, aromatic stacking interaction was not found between phenanthlorine ligand and mono-substituted benzoate ligand or anion. In (â… )-(â…¡) and (â…¤), aromatic stacking interaction between phenanthlorine ligand and multiple-substituted benzoate ligand or anion was found. Based on Hunter-Sanders' model, the addition of substituted group was tend to multiply the polarity of benzene rings and deduce the density ofÏ€electrons, which was helpful to form aromatic stacking interaction.Although the metal ion differed, the supra-molecular structure of (â… ) and (â…¡) was similar which could be used to observe the influence of metal ions toward aromatic stacking. But no obvious distinction was observed.In this paper, we also discussed the role of intermolecular interactions played in building the architecture structures of (â… )-(â…¤): though intermolecular hydrogen bonding, C-H…πand aromatic stacking interaction, in (â… )-(â…¢), guest molecules steadily filled in holes or channels formed by host molecules; the organization of 1D to 3D supra-molecular structure founded in (â…£)-(â…¤) showed that: molecular self-assemble are prone to maximize the use of space and adopt the most close stacking mode.