A new three-dimensional luminescent cobalt (II) metal–organic framework, [Co(Titpe)(bcpf)·(DMF)]·(H2O)2·(DMF) (compound 1, JUST-8) (Titpe = 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethane, bcpf = 4,4′-sulfonyldibenzoic acid; DMF = N, N-dimethylformamide), has been solvothermally synthesized by using CoCl2·6H2O and a mixture of ligands: Titpe ligand and bcpf ligand. Single crystal X-ray analysis reveals that 1 crystallizes in the triclinic system and [Formula: see text] space group with a = 13.2097(14) Å, b = 13.9519(14) Å, c = 14.4413(15) Å, α = 89.949(7)°, β = 70.303(7)°, γ = 80.322(7)°, V = 2465.7(5) Å3, Z = 2, Mr =1032.97, Dc = 1.391 g/cm3, μ = 0.455 mm−1, F(000) = 1070, R = 0.0585, and wR = 0.1540 for 8674 observed reflections ( I > 2σ( I)). Its overall structure is a double-fold interpenetrated framework, and it shows a porosity of 12.97% based on a calculation by PLATON and a 4- c type topological network with the point symbol of {6^5.8}. The Co atom bridges the Titpe ligands to form the one-dimensional chains into a two-dimensional layered structure and then connects the auxiliary ligands to get a three-dimensional structure. Compound 1 showed a blue fluorescence emission with the peak maximum at 431 nm (λex = 314 nm).
