3D/3D Hetero-Interpenetrating Diamondoid Framework and Homo-Interpenetrating pcu Network by a One-Pot Reaction

Two new metal-organic frameworks (MOFs) with novel architectures, namely, [Co-2(NDC)(2)(H2MDP)(2)][(Co(NDC)(H2MDP)] (1) and [Co(NDC)(H2MDP)(0.5)] (2) were synthesized through a one-pot reaction. The metal to ligand ratio was found to influence the formation of the two compounds, and their pure phases were successfully obtained only by adjusting the molar ratios of Co/H2NDC/H2MDP to be 1:1:1 and 2:2:1, respectively [H2NDC = 1,4-naphthalenedicarboxylic acid, H2MDP = methylenebis(3,5-dimethylpyrazole)]. X-ray crystallographic analyses showed that 1 crystallizes as a racemic twin and features an interesting threefold 3D/3D hetero-interpenetrating diamondoid framework with left-handed and right-handed helical chains, whereas 2 displays a 3D twofold homo-interpenetrating pcu network constructed from paddle-wheel secondary building units and H2MDP pillars in a trans conformation. The one-pot synthesis of two or more MOFs with hetero-interpenetration and homo-interpenetration has been rarely reported.