Amine-templated open-framework zinc arsenates of varying dimensionalities: Synthesis, structure, polymorphism, and transformation reactions

作者：Rao V Koteswara; Chakrabarti Sandip; Natarajan Srinivasan^*

来源：Inorganic Chemistry, 2007, 46(25): 10781-10790.

DOI：10.1021/ic7014594

Eight new open-framework zinc arsenates, encompassing the entire hierarchy of open-framework structures, have been prepared hydrothermally. The structures include zero-dimensional, one-dimensional chains, two-dimensional layers, and three-dimensional structures formed through the transformation of the molecular zinc arsenates. The structure of [C6N4H21][Zn(HAsO4)(2)(H2AsO4)], I, is composed of ZnO4 and H(2)ASO(4) units connected through the vertices forming four-membered rings with HASO(4) units hanging from the Zn center. The four-membered rings are connected through the corners forming the one-dimensional chain structures in [C4N2H12][Zn(HASO(4))(2)]center dot H2O, II, and [C5N2H14][Zn(HASO(4))(2)]center dot H2O, III. ZnO4 and AsO4 units form a fully four-connected two-dimensional structure in [C4N2H12][Zn(AsO4)](2), IV. One-dimensional zigzag ladders are connected through HAsO4 units forming two-dimensional layers in [C4N2H12](1.5)[Zn-2(AsO4)(HASO(4))(2)]center dot H2O, V, while the similar building units form a layer with hanging HASO(4) units in the layered arsenate [C6N4H21](6)[Zn-12(HAsO4)(21)], VI. Hanging HASO(4) units are also observed in the polymorphic structures of [C6N3H20][Zn-2(ASO(4))(HAsO4)(2)]center dot 2H(2)O, VII and VIII. Formation of zero-dimensional m onomer, I, a fully four-connected layer, IV, and the polymorphic structures, VII and VIII, are important and noteworthy. The transformation reactions of I indicate that the monomer is reactive and gives rise to structures of higher dimensionalities, indicating a possible Aufbau-type building-up process in these structures.

• 出版日期2007-12-10