Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr(6)O(4)(OH)(4)(bpdc)(6) (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L(1)-L(6) ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L(1)-L(6) ligands. MOFs 1-6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m(2)/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*Ir(III)(dcppy)Cl] (H(2)L(1)), [Cp*Ir(III)(dcbpy)Cl]Cl (H(2)L(2)), and [Ir(III)(dcppy)(2)(H(2)O)(2)]OTf (H(2)L(3)) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h(-1). The [Re(I)(CO)(3)(dcbpy)Cl] (H(2)L(4)) derivatized MOF 4 served as an active catalyst for photocatalytic CO(2) reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H(2)L(4). MOFs 5 and 6 contained phosphorescent [Ir(III)(ppy)(2)(dcbpy)]Cl (H(2)L(5)) and [Ru(II)(bpy)(2)(dcbpy)]Cl(2) (H(2)L(6)) (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, CO(2) 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.

Fe(III)-carboxylate nanoscale metal-organic frameworks (NMOFs) with the MIL-101 structure were synthesized using a solvothermal technique with microwave heating. The ~200 nm particles were characterized using a variety of methods, including SEM, PXRD, nitrogen adsorption measurements, TGA, and EDX. By replacing a percentage of the bridging ligand (terephthalic acid) with 2-amino terephthalic acid, amine groups were incorporated into the framework to provide sites for covalent attachment of biologically relevant cargoes while still maintaining the MIL-101 structure. In proof-of-concept experiments, an optical contrast agent (a BODIPY dye) and an ethoxysuccinato-cisplatin anticancer prodrug were successfully incorporated into the Fe(III)-carboxylate NMOFs via post-synthetic modifications of the as-synthesized particles. These cargoes are released upon the degradation of the NMOF frameworks, and the rate of cargo release was controlled by coating the NMOF particles with a silica shell. Potential utility of the new NMOF-based nano-delivery vehicles for optical imaging and anticancer therapy were demonstrated in vitro using HT-29 human colon adenocarcinoma cells.

A facile hydrothermal synthesis route to N and S, N co-doped graphene quantum dots (GQDs) was developed by using citric acid as the C source and urea or thiourea as N and S sources. Both N and S, N doped GQDs showed high quantum yield (78% and 71%), excitation independent under excitation of 340-400 nm and single exponential decay under UV excitation. A broad absorption band in the visible region appeared in S, N co-doped GQDs due to doping with sulfur, which alters the surface state of GQDs. However, S, N co-doped GQDs show different color emission under excitation of 420-520 nm due to their absorption in the visible region. The excellent photocatalytic performance of the S, N co-doped GQD/TiO2 composites was demonstrated by degradation of rhodamine B under visible light. The apparent rate of S, N:GQD/TiO2 is 3 and 10 times higher than that of N:GQD/TiO2 and P25 TiO2 under visible light irradiation, respectively.

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Photoluminescent graphene quantum dots (GQDs) have received enormous attention because of their unique chemical, electronic and optical properties. Here a series of GQDs were synthesized under hydrothermal processes in order to investigate the formation process and optical properties of N-doped GQDs. Citric acid (CA) was used as a carbon precursor and self-assembled into sheet structure in a basic condition and formed N-free GQD graphite framework through intermolecular dehydrolysis reaction. N-doped GQDs were prepared using a series of N-containing bases such as urea. Detailed structural and property studies demonstrated the formation mechanism of N-doped GQDs for tunable optical emissions. Hydrothermal conditions promote formation of amide between –NH2 and –COOH with the presence of amine in the reaction. The intramoleculur dehydrolysis between neighbour amide and COOH groups led to formation of pyrrolic N in the graphene framework. Further, the pyrrolic N transformed to graphite N under hydrothermal conditions. N-doping results in a great improvement of PL quantum yield (QY) of GQDs. By optimized reaction conditions, the highest PL QY (94%) of N-doped GQDs was obtained using CA as a carbon source and ethylene diamine as a N source. The obtained N-doped GQDs exhibit an excitation-independent blue emission with single exponential lifetime decay.

Chromium(VI) [Cr(VI)] is considered as a severe environmental pollutant, due to its highly toxic and carcinogenic properties. Therefore, low cost, highly sensitive sensors for the determination of Cr(VI) are highly demanded. It is well-known that highly luminescent carbon dots (CDs) have been successfully applied as fluorescent nanosensors for pH, ions, and molecular substances. In the present work, we have demonstrated an on-off fluorescent CD probe for detecting Cr(VI) based on the inner filter effect (IFE) because the absorption bands of Cr(IV) fully covered the emission and excitation bands of CDs. This CD-based nanosensor provides obvious advantages of simplicity, convenience, rapid response, high selectivity, and sensitivity, which have potential application for the detection of Cr(VI) in the environmental industry. In addition, because Cr(VI) can be reduced to low valent chromium species easily by reductant, resulting in the elimination of the IFE and recovery of CD fluorescence, the CD-Cr(VI) mixture could behave as an off-on type fluorescent probe for reductant. We employed ascorbic acid (AA) as an example molecule to demonstrate this off-on type fluorescent probe.

Phosphorescent cyclometalated iridium tris(2-phenylpyridine) derivatives were designed and incorporated into coordination polymers as tricarboxylate bridging ligands. Three different crystalline coordination polymers were synthesized using a solvothermal technique and were characterized using a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, IR spectroscopy, gas adsorption measurements, and luminescence measurements. The coordination polymer built from Ir[3-(2-pyridyl)benzoate](3), 1, was found to be highly porous with a nitrogen BET surface area of 764 m(2)/g, whereas the coordination polymers built from Ir[4-(2-pyridyl)benzoate](3), 2 and 3, were nonporous. The (3)MLCT phosphorescence of each of the three coordination polymers was quenched in the presence of O(2). However, only 1 showed quick and reversible luminescence quenching by oxygen, whereas 2 and 3 exhibited gradual and irreversible luminescence quenching by oxygen. The high permanent porosity of 1 allows for rapid diffusion of oxygen through the open channels, leading to efficient and reversible quenching of the (3)MLCT phosphorescence. This work highlights the opportunity of designing highly porous and luminescent coordination polymers for sensing other important analytes.

A theranostic nanomedicine (CD-Oxa) is synthesized by means of the condensation reaction between the amino groups on the surface of fluorescent carbon dots (CDs) and the carboxyl group of the oxaliplatin derivative Oxa(IV)-COOH. CD-Oxa, which integrates the optical properties of CDs and the anticancer function of oxaliplatin, could be used for simultaneous drug delivery and fluorescent tracking.