Easy-to-implement methods were realized with glucose-based gelators for the efficient removal of aniline/nitrobenzene, and toxic dyes from contaminated water.

Reductive elimination of Cu(III) intermediates is often proposed as a key step in many copper-catalyzed or -mediated formation of C-C or C-heteroatom bonds. However, there still lacks concrete evidence on this key step, mainly because Cu(III) complexes are usually too unstable to be isolated and structurally characterized. In this work, novel organocopper(III) spiro complexes and their analogous organocopper(I) spiro complexes were synthesized and structurally characterized. Single-crystal X-ray structural analysis revealed that the spiro Cu(III) atom adopted a distorted square-planar geometry while its corresponding spiro Cu(I) atom was tetrahedrally coordinated. A redox transformation between these spiro Cu(I) and Cu(III) complexes was experimentally observed by reacting with reductants or oxidants, respectively. As concrete evidence, the organocopper(III) spiro compounds were found to form C-C bonds intramolecularly via reductive elimination.

The construction of branched coumarin dyes based on a 2D-p-A system is focused to optimize the light-harvesting capability and enhance the photovoltaic performance. Three novel coumarin dyes, coded as MS-C, MS-F, and MS-M, respectively, were obtained by incorporating different units (carbazole, fluorene and methyl groups) with different molecular volume and degrees of electrondonating capability into the p-conjugation linker. Through molecular engineering, their lightharvesting capabilities, energy levels and photovoltaic performance were studied systematically. As expected, with the additional donor, especially utilizing strong electron-donating carbazole unit, the IPCE action spectrum of MS-C keeps a high plateau from 390 nm to 580 nm with nearly unity values. Along with the improvement of IPCE, the J sc values of the three dyes were increased by 77% from 7.61 (MS-M) to 13.47 mA cm À2 (MS-C). Using DCA as the co-adsorbed material, the J sc of MS-M was increased while these values were decreased in the cases of branched MS-C and MS-F. This means that the twist structure arising from the branched donors could prevent p-aggregation effectively. More importantly, the V oc was also improved significantly by introducing the additional donor. While the branched 2D-p-A system was constructed, the V oc was sharply increased from 508 (MS-M) to 610 mV (MS-C). Comprehensively, a more than 100% enhancement in overall conversion efficiency (5.53%) was realized by branched MS-C compared to the linear MS-M (2.74%). Although the overall conversion efficiencies of these dyes are not very high, these results will still afford significant value for future development of efficient coumarin sensitizers with high open-circuit voltage.

Three polyanion-containing supramolecular hybrids, (H2bpp)6{Ni[Mo(V)6O13(OH)2(HPO4)3(H2PO4)]2}2·13H2O [1; bpp = 1,3-bis(4-pyridyl)propane], (H2bpp)5{Cd[Mo(V)6O15(HPO4)3(H2PO4)]2}{Cd[Mo(V)6O15(HPO4)4]2}·10H2O (2), (H2bpp)2[Cd(H2O)Cd(H2O)2]2{Cd[Mo(V)6O12(OH)3(HPO4)2(PO4)2]2}·8H2O (3), have been synthesized and characterized. The inorganic moieties in 1-3 belong to the reduced {M[P4Mo(V)6X31]2}(n-) (M = Ni, Cd) clusters. Three supramolecular hybrids exhibit reversible multiple electron-transfer behaviors and have been used as heterogeneous molecular catalysts for the reduction of ferricyanide (Fe(III)) to ferrocyanide (Fe(II)) with Na2S2O3 as a reductant. The experimental results indicate that hybrid materials 1-3 have higher catalytic activity toward the reaction. These low-cost catalysts can effectively decrease the activation energy of this reaction. These values are calculated to be 25.35 kJ·mol(-1) for hybrid 2, 84.11 kJ·mol(-1) for hybrid 1, and 83.14 kJ·mol(-1) for hybrid 3. The reaction mechanism is subjected to a surface-catalytic process.