Syntheses,Structures, Luminescence,and Gas Adsorption Properties of Two New Heterometallic Complexes Involving Alkaline Earth Metals (Ca,Ba)

Two new 3D heterometallic frameworks, Me₂NH₂]CaCd₂(BTC)(HBTC)₂] · 4H₂O ( 1 ) and Ba₁₁Co₂(BTC)₈(μ₃‐OH)₂(μ₂‐H₂O)₆(H₂O)₁₆] ( 2 ) (H₃BTC = 1,3,5‐benzenetricarboxylic acid, Me₂NH₂ = protonated dimethylamine), were synthesized using solvothermal and hydrothermal techniques, respectively. Complex 1 features a 3D microporous framework; it contains hourglass‐like trinuclear CaCd₂(COO)₆] clusters that are bridged by –COO^– groups and form zigzag chains. These chains are further interlinked by the –COO^– groups of BTC^3– ligands into 2D layers with interesting flower‐like configuration, which, in turn, are connected by HBTC^2– ligands to afford the 3D structure. Me₂NH₂⁺ cations not only balance the negative charges of the host framework but also play template roles to fill in the channels, further consolidating the whole framework. The complicated 3D network of complex 2 is constructed by the interconnection of 2D layers, which, in turn, are made of the infinite inorganic chains based on hexanuclear Ba₆] clusters, and these 1D chains are decorated by {CoO₆} octahedrons. Interestingly, the 2D layer can be viewed as a unique structure composed of two different kinds of heart‐shaped rings, which partially overlapped in apical positions to produce a ten‐membered ring window. Moreover, the luminescence properties of 1 – 2 and the gas adsorption property of 1 have also been studied.