Assembly of 63,66-pillared metal-organic bilayers and diamondoid lattices using molecular Li2O2 ring dimers as secondary building units

The lithium aryloxide [4-Br-2,6-Me2C6H2OLi] forms solvated molecular Li2O2 ring dimers in both 1,4-dioxane and 1,3-dioxolane solutions, as determined by NMR spectroscopic and cryoscopic studies. In turn, the geometry of these aggregates controls the architectures of the resulting extended networks upon crystallization from these solvent systems. Specifically, the tetrasolvated dimers act as novel tetrahedral or trigonal nodes to produce the unprecedented 6(3),6(6) pillared bilayer polymer [{(ArOLi)(2)center dot(mu-diox)(2)}center dot{(ArOLi)(2)-(diox)center dot(mu-diox)(1.5)}](infinity) (2) and the three-dimensional dianiondoid framework [(ArOLi)(2)center dot(mu-dioxol)(2)](infinity) (3). The structure of 2 is particularly noteworthy, being composed of two fused hexagonal sheets to form an interrupted diamondoid net.