ABSTRACT
The stability of a photoactivated isonitrosyl state was boosted by confining a pre-designed bicarboxylate ligand with a ruthenium nitrosyl fragment in a 2D metal-organic framework. The novel Zn/Ru-based MOF, {Zn[RuNO(H2O)(inic)2(OH)2]2}·12H2O (inic = isonicotinate), was obtained with enhanced isonitrosyl stability by 30 K (up to 200 K) compared to the related ruthenium-only complex.
ABSTRACT
In contrast to aromatic carboxylates, the coordination polymers based on their perfluorinated analogues are not numerous. Here we present a series of six Zn(ii) coordination polymers of different dimensionalities (1D, 2D, and 3D) and porosities based on octafluorobiphenyl-4,4'-dicarboxylate (oFBPDC2-) and N-containing co-ligands (ur, dabco, and bpy). These complexes are characterized by single-crystal X-ray diffraction, PXRD, FT-IR, elemental analysis, and TGA. The metal-organic frameworks [Zn2(CH3CONH2)2(oFBPDC)2] (1) and [Zn2(oFBPDC)2(dabco)] (4) are shown to be porous with BET surface areas of 470 m2 g-1 and 441 m2 g-1, respectively. In addition, compound 4 shows selectivity factors of 11.3, 4.9 and more than 6 for the binary gas mixtures CO2/N2, CO2/CH4 and benzene/cyclohexane, respectively. The measurements for pressed powders and water droplet give water contact angles of 136° for 4 and 133° for (H2bpy)[Zn2(bpy)(oFBPDC)3] (5). Low water uptake indicates that both 4 and 5 belong to highly hydrophobic solids.
ABSTRACT
Inclusion compounds of photoluminescent hexamolybdenum cluster complexes in the chromium terephthalate metal-organic framework, MIL-101 (MIL, Matérial Institut Lavoisier) were successfully synthesized in two different ways and characterized by means of powder X-Ray diffraction, chemical analysis and nitrogen sorption. Some important functional properties of hexamolybdenum cluster complexes for biological and medical applications, in particular singlet oxygen generation ability, luminescence properties, cellular uptake behavior and cytotoxicity were studied. It was revealed that the inclusion compounds possessed significant singlet oxygen generation activity. The materials obtained showed a low cytotoxicity, thus allowing them to be used in living cells. Confocal microscopy of human larynx carcinoma (Hep-2) cells incubated with the inclusion compounds showed that MIL-101 performed as a nanocarrier adhering to the external cell membrane surface and releasing the cluster complexes which that penetrated into the cells. Moreover, photoinduced generation of reactive oxygen species (ROS) in Hep-2 cells incubated with inclusion compounds was demonstrated. The cluster supported on MIL-101 was shown to possess in vivo phototoxicity.
