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)·(diox)n], M = Li, Na, K, Rb, Cs

The complete series of group 1 metal 4-ethylphenoxide (4-Et-C6H4O–) networks have been synthesized using 1,4-dioxane (diox) as a neutral linker. [{(4-Et-C6H4OLi)4·(diox)2.5}·diox]∞ (1) and [{(4-Et-C6H4ONa)6·(diox)3}∞] (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·diox}∞] (3), [{(4-Et-C6H4ORb)2·(diox)0.5}∞] (4), and [{(4-Et-C6H4OCs)2·(diox)0.5}∞] (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.