Abstract
The cationic metal cage complex (1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]cicosane)cobalt(III), Co(sep)3+ has been investigated as a potential pillaring reagent for Na+-magadiite (Na1.7Si14O27.9(OH)1.9 · 7.6 H2O) a synthetic layered sodium silicate. Reaction of Na+-magadiite with aqueous solutions of Co(sep)Cl3 at 25°C resulted in the binding of Co(sep)3+ cations to the external crystalline surface of the layered silicate. In contrast, an intercalated product exhibiting a 17.6 Å basal spacing was generated by reaction at 100°C.29Si MAS NMR and FT-IR spectroscopy indicate that Co(sep)3+ intercalated reaction products retain the magadiite layer structure. Moreover, scanning electron micrographs of the reaction products showed retention of the original particle morphology, suggesting a topotactic intercalation. However, during intercalation, some of the Co(sep)3+ was found to undergo an unusual demetalation reaction leaving a combination of Co(II) and Co(sep)3+ between the layers. Nitrogen surface area analysis showed that only a small amount of microporous surface existed in the Co(sep)3+ intercalated derivative, suggesting that most of the interlayer space is ‘stuffed’ with cobalt species.
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Dailey, J.S., Pinnavaia, T.J. Intercalative reaction of a cobalt(III) cage complex, Co(sep)3+, with magadiite, a layered sodium silicate. J Incl Phenom Macrocycl Chem 13, 47–61 (1992). https://doi.org/10.1007/BF01076670
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DOI: https://doi.org/10.1007/BF01076670