Fluorescent Cadmium Bipillared-Layer Open Frameworks: Synthesis, Structures, Sensing of Nitro Compounds, and Capture of Volatile Iodine.

Abstract

Fluorescent Cd metal-organic frameworks (MOFs), [Cd2 (dicarboxylate)2 (NI-bpy-44)2 ] (dicarboxylate=benzene-1,4-dicarboxylate (1,4-bdc, 1), 2-bromobenzene-1,4-dicarboxylate (Br-1,4-bdc, 2), 2-nitrobenzene-1,4-dicarboxylate (NO2 -1,4-bdc, 3), biphenyl-4,4'-dicarboxylate (bpdc, 4); NI-bpy-44=N-(pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide)), featuring non- and twofold interpenetrating pcu-type bipillared-layer open structures with sufficient free voids of 58.4, 51.4, 51.5, and 41.4 %, respectively, have been hydro(solvo)thermally synthesized. MOFs 1-4 emitted solid-state blue or cyan fluorescence emissions at 447±7 nm, which mainly arose from NI-bpy-44 and are dependent on the incorporated solvents. After immersing the crystalline samples in different solvents, that is, H2 O and DMSO (1 and 2) as well as nitrobenzene and phenol (1-4), they exhibited a remarkable fluorescence quenching effect, whereas o-xylene and p-xylene (4) caused significant fluorescence enhancement. The sensing ability of MOFs 1-4 toward nitro compounds carried out in the vapor phase showed that nitrobenzene and 2-nitrophenol displayed detectable fluorescence quenching with 1, 2, and 4 whereas 4-nitrotoluene was an effective fluorescence quencher for 1 and 2; this is most likely attributed to their electron-deficient properties and higher vapor pressures. Moreover, MOFs 1-4 are highly reusable for quick capture of volatile iodine, as supported by clear crystal color change and also by immense fluorescence quenching responses owing to the donor-acceptor interaction. Low-pressure CO2 adsorption isotherms indicate that activated materials 1'-4' are inefficient at taking up CO2 .