Metal–Organic Frameworks Constructed from Group 1 Metals (Li, Na) and Silicon-Centered Linkers

A series of “light metal” metal–organic frameworks containing secondary building units (SBUs) based on Li⁺ and Na⁺ cations have been prepared using the silicon-centered linkers Me_<i>x</i>Si­(<i>p</i>-C₆H₄CO₂H)_4‑<i>x</i> (<i>x</i> = 2, 1, 0). The unipositive charge, small size, and oxophilic nature of the metal cations give rise to some unusual and unique SBUs, including a three-dimensional nodal structure built from sodium and oxygen ions when using the triacid linker (<i>x</i> = 1). The same linker with Li⁺ cations generated a chiral, helical SBU, formed from achiral starting materials. One-dimensional rod SBUs are observed for the diacid (<i>x</i> = 2) and tetra-acid (<i>x</i> = 0) linkers with both Li⁺ and Na⁺ cations, where the larger size of Na⁺ compared to Li⁺ leads to subtle differences in the constitution of the metal nodes