The complexation ability of hybrid disilane and ethylene containing crown ether ring systems was analyzed using 1,2-disila[12]crown-4 (1), 1,2-disila[15]crown-5 (2), 1,2-disila[18]crown-6 (3), and 1,2,7,8-tetrasila[12]crown-4 (7). Alkali-metal complexes (Li(+), Na(+), K(+)) were obtained and analyzed via X-ray diffraction. The complex stability of [Li(1,2-disila[12]crown-4)](+) and [Li(1,2,7,8-tetrasila[12]crown-4)](+) was determined, in relation to the lithium complex of [12]crown-4, by density functional theory (DFT) calculations employing the BP86/def2-TZVP level of theory. In solution, the exchange of lithium cations between pure [12]crown-4 and hybrid [12]crown-4 is on even terms, as has been shown from the relative binding affinity of compounds 1 and 7 by means of dynamic proton nuclear magnetic resonance (NMR) spectroscopy.

Syntheses of [K([2.2.2]crypt)](+) salts of binary Pb-Bi Zintl anions and their reaction with ZnPh(2) or Ni(cod)(2), yielding ternary intermetalloid Ni-Pb-Bi or Zn-Pb-Bi clusters, proved the use of binary precursors with fully isoelectronic atoms as an efficient and thus valuable synthetic approach to this class of clusters. (207)Pb NMR and ESI mass spectra provided insight into the solution behavior of the binary or ternary cages.

Metal–organic frameworks are known to contain defects within their crystalline structures. Successful engineering of these defects can lead to modifications in material properties that can potentially improve the performance of many existing frameworks. Herein, we report the high-throughput computational screening of a large experimental metal–organic framework database to identify 13 frameworks that show significantly improved methane storage capacities with linker vacancy defects. The candidates are first identified by focusing on structures with methane-inaccessible pores blocked away from the main adsorption channels. Then, organic linkers of the candidate structures are judiciously replaced with appropriate modulators to emulate the presence of linker vacancies, resulting in the integration and utilization of the previously inaccessible pores. Grand canonical Monte Carlo simulations of defective candidate frameworks show significant enhancements in methane storage capacities, highlighting that rational defect engineering can be an effective method to significantly improve the performance of the existing metal–organic frameworks.

The first hybrid crown ether with two adjacent disilane fragments was synthesized through reaction of O(SiMeCl) (3) with O(CHOH). By means of DFT calculations, the complexation ability of 1,2,4,5-tetrasila[12]crown-4 (7) towards Li was determined to be considerably higher compared to [12]crown-4.