Part I. Layered Double Hydroxides

A new general method for the preparation of well -ordered layered double hydroxides (LDHs), (Mg_ {rm 1-x}Al_{ rm x} (OH)_2) (X^{rm n-}) _{rm n/x}{cdot}yH _2O, interlayered by organic anions has been developed. It is based on the reaction of meixnerite, (Mg_3Al(OH)_8) (OH) cdot2H_2O, with the free acid form of the desired anion--using glycerol as a swelling agent--to yield single crystalline products that are not readily available by conventional synthetic methods. The (Mg_3Al(OH) _8) -adipate and -p-toluenesulfonate derivatives undergo facile ion exchange reactions with Keggin-type (XM_{12}O_ {40}) ^{rm n -} or lacunary (XM_{11 }O_{39}) ^{rm m-} polyoxometalates (POMs) to form well-ordered, microporous pillared derivatives with the highest N_2 BET surface areas reported to date, namely 107 and 155 m^2 /g, respectively. Meixnerite, (Mg_3Al(OH) _8) (OH) cdot2H _2O, has unexpectedly been found to undergo similar ion exchange reactions, in a topotactic way, with retention of the structure of the intercalated POMs. The meixnerite was conveniently prepared for the first time from calcination of (Mg_3Al(OH) _8) (CO_3) _{0.5}{cdot}2H _2O and aqueous hydrolysis of the resulting NaCl-type solid solution. Metal carbonyl clusters have also been examined for ion-exchange (i.e., { (Pt _3(CO)_6) _{rm n}}^ {2-}) in these LDH-precursors. This chemistry is compared with the surface chemistry of (Mg_3 Al(OH)_8) (X^ {rm n-}) _{ rm 1/n}{cdot}2H _2O (X = CO_3^{2 -} or OH^{-}). It has been shown that the surface hydrolysis reaction: CO _3^{2-} + H _2O longrightarrow HCO_3^{-} + OH ^-, causes reductive condensation reactions of neutral carbonyl clusters with the LDH. The reactions were as efficient as with Na metal in solution. In part II of this work, Li-fluorohectorite, has been pillared with titanium polyoxocations derived from the acidic hydrolysis of TiCl_4 or Ti(i-OC_3H_7) _4. Raman spectroscopy of the product indicates that the pillars have a structure analogous to TiO_2(B) phase. It is proposed that the pillars consist of aggregates of condensed (Ti _8O_{12} (H_2O)_{24 }) ^{8+} cations.