Hexagons, Squares and Cubes in the Chemistry of Alumazene, Aluminophosphonates, and Lanthanide Coordination Polymers
| Authors | |
|---|---|
| Year of publication | 2005 |
| Type | Article in Proceedings |
| Conference | Chimie et Art |
| MU Faculty or unit | |
| Citation | |
| Field | Inorganic chemistry |
| Keywords | Alumazene; Aluminophosphonates; Lanthanides; Coordination Polymers |
| Description | Hexagonal and square arrangements possess the highest symmetry among two-dimensional patterns while the cube is one of the most symmetrical bodies in the three-dimensional space. It is always pleasing for a chemist to synthesize compounds with such simple structural motifs and elucidate their crystal structures. We studied the reactivity of alumazene, which is an inorganic benzene analog. Its hexagonal molecule undergoes dealkylsilylation reactions with a variety of trimethylsilyl esters of inorganic acids and provides bicyclic, spirocyclic, and adamantane-like cage molecules. Interestingly, the sulfonate derivative forms a hexagonal supramolecular structure in the solid phase. Phosphonic acids react with trialkylalanes and form cage-like molecules. The majority of derivatives features a cubic Al4P4O8 core with peripheral organic substituents. Examples of oligomers with a hexagonal prism core are also known. Square-like molecular aluminophosphates, -phosphonates, and -phosphinates serve as precursors in nonhydrolytic sol-gel routes to aluminophosphate materials. Aminoisopropyl phosphonic acid forms with aluminum under hydrothermal conditions in the presence of a fluoride mineralizer a cubic molecule Al8F12[H3N(CH3)2CPO3]12. Its identity was confirmed by ESI-MS and X-ray diffraction analysis. Coordination polymers of bis(diphenylphosphino)ethane dioxide Ph2P(O)-CH2CH2-P(O)Ph2 with lanthanide salts were shown to consist of either binuclear complex molecules or two-dimensional infinite layers. The actual arrangement depends on the nature of lanthanide ion, the counterion involved and the employed reaction conditions, such as temperature and solvent. Brick wall, parquet floor, and honeycomb architectures were identified in the solid state by single crystal X-ray diffraction. |
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