Pd-Containing Organo­polyoxo­metalates Derived from Dawson Polyoxo­metalate [P₂W₁₅V₃O₆₂]^9–: Lewis Acidity and Dual Site Catalysis

Grafting of a palladium complex to the Dawson vanado­tungstate polyanion [P₂W₁₅V₃O₆₂]^9– via an organic ligand generates a large family of pincer-type hybrid polyoxometalates. The palladium-POM derivatives have dual catalytic properties. Unlike their parent inorganic polyanions, they catalyze allylations while retaining their oxidant character, which leads to single-pot dual site catalysis. This opens a new route for multicatalytic reactions

Expeditive Access to 2‑Substituted 4<i>H</i>‑Pyrido[1,3]oxazin-4-ones <i>via</i> an Intramolecular O‑Arylation

Unreported 2-substituted 4<i>H</i>-pyrido[<i>e</i>][1,3]oxazin-4-ones are synthesized <i>via</i> an unprecedented intramolecular O-arylation of <i>N</i>-aroyl- and <i>N</i>-heteroaroyl-(iso)nicotinamides under microwave irradiations, in good to excellent yields. The broad applicability was demonstrated by 24 examples with a variety of substituents at the 2-position of the final compounds and 3 possible positions for the nitrogen atom of the pyridine ring. In addition, transformation of one of these compounds into 2-hydroxypyridyl-substituted 1,2,4-triazole and 1,2,4-oxazinone was realized. This approach opens a rapid access to a new bicyclic heteroaromatic chemical series with high potential in medicinal chemistry

Synthesis, Photophysical Properties, and Living Cell Imaging of Theranostic Half-Sandwich Iridium–4,4-Difluoro-4-bora‑3<i>a</i>,4<i>a</i>‑diaza‑<i>s</i>‑indacene (BODIPY) Dyads

We report the synthesis, characterization, and photophysical properties of two new cyclometalated half-sandwich iridium­(III) complexes having the general formula [(η⁵-Cp*)­Ir­(ppy)­Z]­PF₆ where η⁵-Cp* = pentamethylcyclopentadienyl and ppy = 2-phenyl-pyridine as C^∧N-chelating ligand and <i>Z</i> = 3- or 4-pyridyl-BODIPY (BODIPY = 4,4-difluoro-4-bora-3<i>a</i>,4<i>a</i>-diaza-<i>s</i>-indacene dye containing a 3- or 4-pyridyl group at the meso position). The molecular structure of both complexes has been determined by X-ray crystallography. The photophysical properties of the dyads were investigated and compared to the pyridyl-BODIPY precursors. Antiproliferative studies demonstrated that one of the compounds was highly active with submicromolar IC₅₀ on a panel of cancer cell lines. The replacement of the chlorido ligand by the pyridyl-BODIPY increased the lipophilicity of the complexes and slowed down the hydrolysis rate, which in turn increased the cytotoxicity of the metallodrug candidate. For the first time, cell uptake of one of the dyads was monitored by living cell fluorescence imaging. Interestingly, extremely fast internalization was observed the rate of which was temperature-dependent

Synthesis, Photophysical Properties, and Living Cell Imaging of Theranostic Half-Sandwich Iridium–4,4-Difluoro-4-bora‑3<i>a</i>,4<i>a</i>‑diaza‑<i>s</i>‑indacene (BODIPY) Dyads

We report the synthesis, characterization, and photophysical properties of two new cyclometalated half-sandwich iridium­(III) complexes having the general formula [(η⁵-Cp*)­Ir­(ppy)­Z]­PF₆ where η⁵-Cp* = pentamethylcyclopentadienyl and ppy = 2-phenyl-pyridine as C^∧N-chelating ligand and <i>Z</i> = 3- or 4-pyridyl-BODIPY (BODIPY = 4,4-difluoro-4-bora-3<i>a</i>,4<i>a</i>-diaza-<i>s</i>-indacene dye containing a 3- or 4-pyridyl group at the meso position). The molecular structure of both complexes has been determined by X-ray crystallography. The photophysical properties of the dyads were investigated and compared to the pyridyl-BODIPY precursors. Antiproliferative studies demonstrated that one of the compounds was highly active with submicromolar IC₅₀ on a panel of cancer cell lines. The replacement of the chlorido ligand by the pyridyl-BODIPY increased the lipophilicity of the complexes and slowed down the hydrolysis rate, which in turn increased the cytotoxicity of the metallodrug candidate. For the first time, cell uptake of one of the dyads was monitored by living cell fluorescence imaging. Interestingly, extremely fast internalization was observed the rate of which was temperature-dependent