<i>meso</i>‐(2‐Pyridyl)‐boron(III)‐subporphyrin: Perimeter Iridium(III) Coordination

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<jats:title>Abstract</jats:title><jats:p>Peripherally metalated porphyrinoids are promising functional π‐systems displaying characteristic optical, electronic, and catalytic properties. In this work, 5‐(2‐pyridyl)‐ and 5,10,15‐tri(2‐pyridyl)‐B<jats:sup>III</jats:sup>‐subporphyrins were prepared and used to produce cyclometalated subporphyrins by reactions with [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub>, which proceeded through an efficient C−H activation to give the corresponding mono‐ and tri‐Ir<jats:sup>III</jats:sup> complexes, respectively. While the mono‐Ir<jats:sup>III</jats:sup> complex was obtained as a diastereomeric mixture, a <jats:italic>C</jats:italic><jats:sub>3</jats:sub>‐symmetric tri‐Ir<jats:sup>III</jats:sup> complex with the three Cp*‐units all at the concave side was predominantly obtained in a high yield of 90 %, which displays weak NIR phosphorescence even at room temperature in degassed CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>, differently from the mono‐Ir<jats:sup>III</jats:sup> complexes.</jats:p>

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