Abstract

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)-BIII -subporphyrins were prepared and used to produce cyclometalated subporphyrins by reactions with [Cp*IrCl2 ]2 , which proceeded through an efficient C-H activation to give the corresponding mono- and tri-IrIII complexes, respectively. While the mono-IrIII complex was obtained as a diastereomeric mixture, a C3 -symmetric tri-IrIII 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 CH2 Cl2 , differently from the mono-IrIII complexes.

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