Molecular engineering of microporous crystals: (IV) Crystallization process of microporous aluminophosphate AlPO4-11

The products of microporous aluminophosphate AlPO4-11 crystallized for different periods of time were freeze-dried and characterized by XRD and NMR techniques. Six crystallographically distinct Al- and P-centered large fragments and 34 small fragments of dimer (Al–P), trimer (Al–P–Al and P–Al–P), tetramer (Al–P3 and P–Al3), pentamer (Al–P4 and P–Al4), and 4- and 6-membered rings were extracted from the framework of AlPO4-11. Each of the six large fragments contained two completed coordination layers surrounding the centered atom. The shielding tensors of the Al and P atoms of the fragments were calculated using the quantum mechanics density functional theory. The experimentally observed chemical shifts of Al or P from the well-crystallized AlPO4-11 were assigned to the shielding tensors of the center atoms of the six large fragments and were further used as references in the determination of the chemical shifts of the Al or P atoms in the small fragments. A comparison of the calculated chemical shifts of the Al and P atoms in the small fragments to the experimental data of the products isolated at different crystallization periods suggested that the fragments of dimers, trimers of the form Al–P–Al, tetramers of the form P–Al3, and pentamers may exist in the crystallization process of AlPO4-11. On the basis of these observations regarding the putative small fragments, a possible crystallization process of AlPO4-11 was proposed.

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► Possible fragments formed in crystallization were extracted from AlPO4-11.
► Chemical shift of the small fragments were calculated.
► Calculated results were compared with the experimentally observed data.
► Sixteen small fragments that may exist in the crystallization process were identified.
► A method to identify the possible fragments formed in the synthesis is developed.