A comparative catalytic study using different metal ions by incorporating functionalized metallosalen into the lacunary position of Keggin polyoxometalate

Multi-Electron Visible Light Photoaccumulation on a Dipyridylamine Copper(II)–Polyoxometalate Conjugate Applied to Photocatalytic Generation of CF3 Radicals

“…37,38 Among these various examples, a few have studied the influence of the POM on the catalytic properties of tethered classical transition metal catalysts. Various advantages of the hybrids, including improved recyclability, 39 electronic delocalization, 40 tunability, 40,41 protection against degradation, 42,43 milder conditions, 44 dual Lewis acid-oxidation catalysis, 45 While some important disorder, notably on the TBA cations and one of the pyridine ring, did exist, the X-ray diffraction study clearly showed the successful grafting of the TrisDPA moiety on the POM via V−O−C bond formation. Interestingly, one can measure a fairly short distance of 3.32(3) Å between the tertiary amine of the TrisDPA moiety and the surface of the POM (defined as the average plane between the six oxygen atoms on top of the vanadium-oxo triad): this should favor a strong electronic communication between the POM skeleton and the grafted complex (Figure 1).…”

“…Yet, DT only absorbs in the UV range and can only be functionalized through an electrostatic association with a co-catalyst, while numerous POMs can be modified through the covalent anchorage of an organic/organometallic moiety to the POM framework. , Among these various examples, a few have studied the influence of the POM on the catalytic properties of tethered classical transition metal catalysts. Various advantages of the hybrids, including improved recyclability, electronic delocalization, tunability, , protection against degradation, , milder conditions, dual Lewis acid-oxidation catalysis, or simply synergy improving yields, have been observed . Moreover, some of these hybrid POMs display also appealing photophysical properties. − …”