Structural chemistry of metal inorganic 3D MT frameworks. Templated nanoclusters-precursors Ga-2(PO4)(2)F-2 and Ga-2(PO4)(2)(HF)F-2 and self-assembly of crystalline gallophosphate structures (NH4)(2)[Ga-2(PO4)(2)F-2](KTP-Type) and (NH4)(2)[Ga-2(PO4)(2)(HF)F-2] (p-KTP-Type)

作者：Shevchenko V Ya^*; Blatov V A; Ilyushin G D

来源：Glass Physics and Chemistry, 2015, 41(6): 561-571.

DOI：10.1134/S1087659615060127

• metal inorganic 3D MT-frameworks
• self-assembly of crystalline structures
• templated nanoclusters-precursors
• gallophosphate structural types (NH4)(2)[Ga-2(PO4)(2)F-2] (KTP-type) and (NH4)(2)[Ga-2(PO4)(2)(HF)F-2] (p-KTP-type)

The article discusses the structural chemistry of metal inorganic microporous 3D MT-frameworks of M-octahedra and T-tetrahedra. Geometric and topological simulation has been applied to topologically different suprapolyhedral M2T2 clusters of two octahedra and two tetrahedral, with the hierarchical structure presented in the form of two-colorable graphs. The obtained data have been used during the search for clusters-precursors of metal inorganic microporous 3D MT-frameworks in the arranged database of crystalline MT-structures (13455 compounds, ToposPro program package). For gallophosphates of close chemical composition (NH4)(2)[Ga-2(PO4)(2)F-2] (KTP-type), (NH4)(2)[Ga-2(PO4)(2)(HF)F-2] (p-KTP-type), the complete 3D reconstruction of the cluster self-assembly of crystalline structures has been performed: nanocluster-precursor S (3) (0) -primary chain S (3) (1) -microlayer S (3) (2) -microframework S (3) (3) . The simulation involves the methods of combinatorial topology analysis based on plotting a basic 3D net of zeolite in the form of a graph, the nodes of which correspond to the position of the gravity centers of clusters-precursors Ga-2(PO4)(2)F-2 for KTP and Ga-2(PO4)(2)(HF)F-2 for p-KTP. Both for KTP and for p-KTP the same type of crystal forming 2D nets 333344 + 3344 (1: 1) have been set. Various variants of the complementary bonding of the 2D nets led to the formation of basic 3D nets with CN = 10 (KTP) and 8 (p-KTP). For the first time the functional role of NH4 clusters-templates, which form hydrogen bonds with the O and F atoms and which fix the relative position of the two Ga-2(PO4)(2)F-2 and Ga-2(PO4)(2)(HF)F-2 clusters, has been considered.

• 出版日期2015-11