Multifunctional Fourfold Interpenetrating Diamondoid Network: Gas Separation and Fabrication of Palladium Nanoparticles

A fourfold interpenetrating diamondoid network, [{[Ni(cyclam)] 2 (mtb)} n ] ⋅ 8 n  H 2 O ⋅ 4 n  DMF ( 1 ) (MTB=methanetetrabenzoate, DMF=dimethylformamide), has been assembled from [Ni(cyclam)][ClO 4 ] 2 (cyclam=1,4,8,11‐tetraazacyclotetradecane) and methanetetrabenzoic acid (H 4 MTB) in DMF/H 2 O (7:3, v/v) in the presence of triethylamine (TEA). Despite the high‐fold interpenetration, 1 generates 1D channels that are occupied by water and DMF guest molecules. Solid 1 , after removal of guest molecules, exhibits selective gas adsorption behavior for H 2 , CO 2 , and O 2 rather than N 2 and CH 4 , suggesting possible applications in gas separation technologies. In addition, solid 1 can be applied in the fabrication of small Pd (2.0±0.6 nm) nanoparticles without any extra reducing or capping agent because a Ni II macrocyclic species incorporated in 1 reduces Pd II ions to Pd 0 on immersion of 1 in the solution of Pd(NO 3 ) 2 ⋅ 2 H 2 O in MeCN at room temperature.