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-C(6)H(4)O(-)) networks have been synthesized using 1,4-dioxane (diox) as a neutral linker. [{(4-Et-C(6)H(4)OLi)(4)·(diox)(2.5)}·diox](∞) (1) and [{(4-Et-C(6)H(4)ONa)(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 Li(4)O(4) cubanes acting as nodes, whereas compound 2 forms a primitive cubic network (pcu) with Na(6)O(6) hexameric nodes. [{(4-Et-C(6)H(4)OK)(3)·diox}(∞)] (3), [{(4-Et-C(6)H(4)ORb)(2)·(diox)(0.5)}(∞)] (4), and [{(4-Et-C(6)H(4)OCs)(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.