Oxyacid-Containing Molecular Compounds And Their Supramolecular Metal Complexes Based Upon Chemical Modification Resorcin[4]Arenes

In recent years, with the extensive application of the supramolecular framework in the pharmaceutical intermediates, gas adsorption and storage, catalysis and so on, it is very important to explore the synthesis of supramolecular complex of calixarene. The aim of this study is to explore the synthesis conditions of resorcin[4]arene complexes. First, we synthesized three kinds of oxyacid-containing molecular compounds based upon chemical modification of resorcin[4]arene, that is, resorcin[4]arene methylene sulfonic acid derivatives(2a-2c), resorcin[4]arene carboxylic acid derivatives(5a-5c), and resorcin[4]arene phosphate derivatives(7a-7c). All of the compound were well characterized by 1H NMR, FT-IR spectroscopies and element analyses, and the intermediates 4b(tetrabromo resorcin[4]arene cavitands), resorcin[4]arene carboxylic acid derivatives 5b(C- propyl- 2- carboxyl resorcin[4]arene) and its isomer 5b' were characterized by single-crystal X-ray diffraction, determined their crystal structure. In the structure of two isomers 5b and 5b' of carboxylate ligands, the way of molecular stacking is different, although they are all connected through O-H…O hydrogen bond. In the structure of 5b, the molecules are arranged in a cup opening to the cup and a cup bottom to the bottom of the cup, forming a double molecular structure, while in the structure of 5b', all of the molecules are aligned in a direction.Second, based on the synthesis, we conducted a large number of coordination reaction experiments, exploring the coordination conditions of the three kinds of resorcin[4]arene derivatives containing oxyacid with alkali metals, alkaline earth metals and transition metal, and crystallization conditions of their complexes, and got three supramolecular metal complexes: complexe8(C96H127O40Cl4S8Co), complexe9(C100H134O42Cl3S8Cr) and complexe10(C96H90O32Cu3). The single crystals of these three complexes were characterized by X- ray single crystal diffraction. In complexes 8 and 9, sulfonic acid ligands formed a dimer structure by coordination with metal salts, and the dimer are connected by intermolecular hydrogen bonds to form a double-layer molecular structure. And in complexes 10, each carboxylate ligands connected to two other molecules through two carboxyl which have different coordination modes with copper ions coordinating to copper ions to form a one-dimensional chain structure. All of the three supramolecular framework complexes have hollow structure, and we will make further exploration on their application properties.