Molecule-ion interaction and its effect on coordination interaction.

The present work revealed the presence of the molecule-ion interaction between ethylenediaminetetraacetic acid disodium salt (Na(2)H(2)EDTA) and ß-cyclodextrin (CD) on the basis of observable changes in crystal patterns and thermal behaviors before and after interaction. Results from electric conductivity measurements confirmed this presence and showed that the extent of the molecule-ion interaction was associated with the concentration of ß-CD. More importantly, the molecule-ion interaction led to a decreased coordination interaction of Na(2)H(2)EDTA and copper chloride, and this decrease exhibited a concentration dependence of ß-CD. Similar phenomena were also observed in the case of several analogs of Na(2)H(2)EDTA by UV-vis spectroscopy. A possible explanation was proposed on the basis of the hypothesis that there was a competitive relationship between the molecule-ion interaction and the coordination interaction. Further, nuclear magnetic resonance measurements provided important information on the difference in interaction modes of ß-CD with H(2)EDTA(2-) and [Cu(EDTA)](2-). We are of the opinion that the results would provide a significant bridge between coordination chemistry and supramolecular chemistry and help us further understand factors related to different interactions in multicomponent systems.

Noncovalent interaction of polyethylene glycol with copper complex of ethylenediaminetetraacetic acid and its application in constructing inorganic nanomaterials.

In this study, we try to answer a fundamental question: what is the consequence of the noncovalent interaction between a polymer and a coordination compound? Here, polyethylene glycol (PEG-4000, PEG-b) and copper complex of ethylenediaminetetraacetic acid (H(2)CuY) were employed to solve this problem. A novel adduct (CEP) between H(2)CuY and PEG-b was prepared. Our results indicated several interesting findings. First, the introduction of H(2)CuY had no effect on the stacking structure of PEG-b but led to a large change in surface structure of the polymer. Second, there was a significant difference (117 K) in the maximum degradation temperature between the PEG and the CEP, suggesting that the noncovalent interaction can drastically improve the thermal stability of the PEG. Third, sintering experiments showed that H(2)CuY and CEP produced completely different decomposition products. The former formed Cu crystals in nitrogen and CuO in air, but the latter generated Cu and CuCl crystals with good crystallinity, respectively. Finally, three independent measurements: viscosity, conductivity and nuclear magnetic resonance in solution, provided useful information and insights from both sides of the noncovalent interaction. Probable interaction mechanisms and interaction sites were proposed. We consider that the current research could create the foundation for a new understanding of how the noncovalent adduct interaction between a metallic complex and a polymer relates to the change in physical and chemical properties of the adducted components.

Formation, characterization, and thermal degradation behavior of a novel tricomponent aggregate of beta-cyclodextrin, ferrocene, and polypropylene glycol.

A tricomponent aggregate PPG-Fc-beta-CD formed by polypropylene glycol (PPG), ferrocene (Fc), and beta-cyclodextrin (beta-CD) was obtained and characterized by a series of physical methods, such as (1)H nuclear magnetic resonance, flame atomic absorption spectrometry, high performance liquid chromatography, UV-vis absorption spectroscopy, thermogravimetry, and gas chromatography coupled to time-of-flight mass spectrometry. First, the tricomponent aggregate exhibited a component ratio of 1:28:32 (PPG/Fc/beta-CD) in the solid state, and showed a completely different order in thermal stability when compared with beta-CD: under a nitrogen atmosphere, beta-CD > PPG-Fc-beta-CD, and in a vacuum, PPG-Fc-beta-CD > beta-CD. Second, the appearance of two peculiar points p and q at the end of TG curve of the aggregate gave a strong impression that the degradation rate further increased after the sharp decomposition of the aggregate reached point p and the amount present in the residual fraction at point q about 780.0 K was lower than 1%, both of which were rather different from those reported previously. This finding implied that the molecular assembly resulting from the binding interaction among Fc, PPG, and beta-CD induced more efficiently the degradation of each of them. Third, an interesting phenomenon was found that the order of thermal release of the three assembled components in PPG-Fc-beta-CD was Fc > beta-CD > PPG. Results of this study provide some insight into an initial attempt to construct a supramolecule among a polymer, a coordination compound, and an organic compound.