Inorganic Chemistry, Vol.51, No.2, 1020-1027, 2012
Effects of the Alkali-Metal Cation Size on Molecular and Extended Structures: Formation of Coordination Polymers and Hybrid Materials in the Homologous Series [(4-Et-C6H4OM)center dot(diox)(n)], M = Li, Na, K, Rb, Cs
The complete series of group 1 metal 4-ethylphenordde (4-Et-C6H4O-) networks have been synthesized using 1,4-dioxane (diox) as a neutral linker. [{(4-Et-C6H4OLi)(4)center dot(diox)(2.5)}center dot diox](infinity) (1) and [{(4-Et-C6H4ONa)(6)center dot(diox)(3)}(infinity)] (2) form 2D and 3D networks, respectively, composed of discrete aggregates linked by diox. Compound 1 forms a hexagonal layered structure with Li4O4 cubanes acting as nodes, whereas compound 2 forms a primitive cubic network (pcu) with Na6O6 hexameric nodes. [{(4-Et-C6H4OK)(3)center dot diox}(infinity)] (3), [{(4-Et-C6H4ORb)(2)center dot(diox)(0.5)}(infinity)] (4), and [{(4-Et-C6H4OCs)(2)center dot(diox)(0.5)}(infinity)] (5) are composed of isostructural 1D inorganic rods that are linked through diox to form pcu-type networks. Compound 5 is the first example of a network built from cesium inorganic rods.