Selective inclusion of PO _4 ~(3-) within persistent dimeric capsules of a tris(thiourea) receptor and evidence of cation/solvent sealed unimolecular capsules

摘要

A tren-based tris(thiourea) receptor, L with electron-withdrawing p-nitrophenyl terminals has been established as a competent hydrogen-bonding scaffold that can selectively encapsulate PO _4 ~(3-) within persistent and rigid dimeric capsules, assembled by aromatic π-stacking interactions between the receptor side-arms. A quaternary ammonium salt of PO _4 ~(3-) capsules (complexes 1 and 1b, 2:1 host-guest) can reproducibly be obtained in quantitative yields by a solution-state deprotonation of [HL] ~+ moieties and a bound HPO _4 ~(2-) anion of complex 1a (HPO _4 ~(2-) complex of protonated L, 2:1 host-guest), induced by the presence of a large excess of anions such as HCO _3 ~-, CH _3CO _2 ~-, and F ~-. Qualitative as well as quantitative ~1H and ~(31)P NMR experiments (DMSO-d _6) have been carried out in detail to demonstrate the selective and preferential inclusion of PO _4 ~(3-) by L in solution-states. Competitive crystallization experiments performed in the presence of an excess of anions such as HCO _3 ~-, HSO _4 ~-, CH _3CO _2 ~-, NO _3 ~- and halides (F ~- and Cl ~-) further establish the phenomenon of selective PO _4 ~(3-) encapsulation as confirmed by ~1H NMR, ~(31)P NMR, FT-IR and powder X-ray diffraction patterns of the isolated crystals. X-ray structural analyses and ~(31)P NMR studies of the isolated crystals of phosphate complexes (1, 1a and 1b) provide evidence of the binding discrepancy of inorganic phosphates with protonated and neutral form of L. Furthermore, extensive studies have been carried out with other anions of different sizes and dimensions in solid- and solution-states (complexes 2a, 3, 4 and 5). Crystal structure elucidation revealed the formation of a solvent (DMSO) sealed unimolecular capsule in the F ~- encapsulated complex, 2a (1:1 host-guest), a CO _3 ~(2-) encapsulated centrosymmetric molecular capsule in 3 (2:1 host-guest) and a cation (tetrabutylammonium) sealed SO _4 ~(2-) encapsulated unimolecular capsule in 4 (1:1 host-guest). 2D-NOESY NMR experiments carried out on these capsule complexes further confirm the relevant binding stoichiometry of complexes (2a-4) except for the PO _4 ~(3-)-encapsulated complex (1b) which showed a 1:1 host-guest stoichiometry in solution.