Carbonate and phosphite encaged in frameworks constructed from square lanthanum aminopolycarboxylates and sodium chloride.

Novel additives of lanthanum aminopolycarboxylates with inorganic anions, Na12n[La(edta)L]4n·8nNaCl·4nH2O (1: L = HPO32-; 2: L = CO32-) and K12n[La(cdta)(CO3)]4n·35nH2O (3) (H4edta = ethylenediaminetetraacetic acid; H4cdta = cyclohexanediaminetetraacetic acid), were obtained in alkaline solution. Structural analyses reveal that 1 and 2 are isomorphous and contain interesting square structures. HPO32- (CO32-) was encaged in the constructed tetranuclear frameworks. Tetranuclear lanthanum ethylenediaminetetraacetate was further encaged in superstructures of sodium chloride. 3 has a similar square structure, in which edta is replaced by cdta. All complexes are fully characterized via elemental, FT-IR, NMR, thermogravimetric and structural analyses. Solution 13C NMR spectra show that 1 and 2 dissociate into mononuclear units in water. Interestingly, 2 possesses 3.7 Å diameter holes inside its crystals, which can adsorb a small amount of O2 or CO2 selectively. The amounts of O2 and CO2 adsorbed increase gradually from 0.32 and 0.38 mg g-1 at 0.4 bar to 15.90 and 10.54 mg g-1 at 29.9 bar, respectively.