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The article new approaches that can be used for the synthesis and designing of various different phosphorescent coordination polymers. These polymers are shown to be extremely porous and hence can be used widely for oxygen sensing and several other techniques.

The synthesis and characterization of Fe(III)-carboxylate nanoscale metal-organic frameworks (NMOFs) with the MIL-101 structure is reported. The potential use of the newly obtained NMOF-based nanodelivery vehicles for optical imaging and anticancer therapy is also demonstrated in vitro by using HT-29 human colon adenocarcinoma cells.

Catalytically competent Ir, Re, and Ru complexes H2L1- H2L6 with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr6O4(OH)4(bpdc)6 (UiO-67, bpdc = para-biphenyl- dicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L1-L6 ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L1-L6 ligands. MOFs 1-6 were isostructuraj to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m2/g. MOFs 1-6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1-3 containing [Cp*IrIII(dcppy)Cl] (H2L1), [Cp*Irhl(dcbpy)Cl] Cl (H2L2), and [1rIII(dcppy)2(H2O)2] OTf (H2L3) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxyljc acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h1. The {Re'(CO)3(dcbpy)cl] (H2L4) derivatized MOF 4 served as an active catalyst for photocatalytic CO2 reduction with a total turnover number (TON? of 10.9, three times higher than that of the homogeneous complex H2L4. MOFs S and 6 contained phosphorescent [1r1' (ppy)2(dcbpy)]cl (H2L5) and {Ru"(bpy)2(dcbpy)]Cl2 (}{2L6) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO2 reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes. The stability of the doped UiO-67 catalysts under catalytic conditions was also demonstrated by comparing PXRD patterns before and after catalysis. This work illustrates the potential of combining molecular catalysts and MOF structures in developing highly active heterogeneous catalysts for solar energy utilization. [ABSTRACT FROM AUTHOR]

Porous cross-linked polymers (PCPs) with phosphorescent [Ru(bpy)3]2+ and [Ir(ppy)2(bpy)]+ building blocks were obtained via octacarbonyldicobalt (Co2-(CO)8)-catalyzed alkyne trimerization reactions. The resultant Ruand Ir-PCPs exhibited high porosity with specific surface areas of 1348 and 1547 m²/g, respectively. They are thermally stable at up to 350 °C in air and do not dissolve or decompose in all solvents tested, including concentrated hydrochloric acid. The photoactive PCPs were shown to be highly effective, recyclable, and reusable heterogeneous photocatalysts for aza-Henry reactions, α-arylation of bromomalonate, and oxyamination of an aldehyde, with catalytic activities comparable to those of the homogeneous [Ru(bpy)3]2+ and [Ir(ppy)2(bpy)]+ photocatalysts. This work highlights the potential of developing photoactive PCPs as highly stable, molecularly tunable, and recyclable and reusable heterogeneous photocatalysts for a variety of important organic transformations. [ABSTRACT FROM AUTHOR]