Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

Molecules. 2022 Sep 15;27(18):6003. doi: 10.3390/molecules27186003.

Abstract

Heteroleptic cyclometalated iridium (III) complexes (1-3) containing di-pyridylamine motifs were prepared in a stepwise fashion. The presence of the di-pyridylamine ligands tunes their electronic and optical properties, generating blue phosphorescent emitters at room temperature. Herein we describe the synthesis of the mononuclear iridium complexes [Ir(ppy)2(DPA)][OTf] (1), (ppy = phenylpyridine; DPA = Dipyridylamine) and [Ir(ppy)2(DPA-PhI)][OTf] (2), (DPA-PhI = Dipyridylamino-phenyliodide). Moreover, the dinuclear iridium complex [Ir(ppy)2(L)Ir(ppy)2][OTf]2 (3) containing a rigid angular ligand "L = 3,5-bis[4-(2,2'-dipyridylamino)phenylacetylenyl]toluene" and displaying two di-pyridylamino groups was also prepared. For comparison purposes, the related dinuclear rhodium complex [Rh (ppy)2(L)Rh(ppy)2][OTf]2 (4) was also synthesized. The x-ray molecular structure of complex 2 was reported and confirmed the formation of the target molecule. The rhodium complex 4 was found to be emissive only at low temperature; in contrast, all iridium complexes 1-3 were found to be phosphorescent in solution at 77 K and room temperature, displaying blue emissions in the range of 478-481 nm.

Keywords: X-ray structural determination; blue emitters; phosphorescent iridium complexes.

Grants and funding

This research has been funded in part by grants from: The Italian Ministry of Economic Development (MiSE)—Mission Innovation Programme (Italian Energy Materials Acceleration Platform, IEMAP); The Italian National Research Council (CNR)—CNR-CNRS Joint International Laboratory Projects (d10 Metal Architectures for Green Lighting, Photoredox Catalysis and Remote Sensing, D10-GREEN); and The Italian National Research Council (CNR)—Research Projects @CNR (Piezo-Phototronic Integrated Devices for the Reduction of CO2 to Liquid Solar Fuels, RIPRESA).