Triplet-Triplet Energy Transfer in Bis-Cyclometalated Iridium Complexes with Pyrene-Substituted Isocyanides

Nonlinear optical (NLO) materials are able to modulate responses of electromagnetic radiation, leading to phenomena critical to modern telecommunications technologies. The last two decades have seen significant advances in the area of molecular nonlinear chromophores, particularly with respect to reverse-saturable absorption (RSA). Here, we introduce a strategy for intense excited-state absorption (ESA) that involves bis-cyclometalated iridium complexes with isocyanide ancillary ligands decorated with pyrene triplet acceptors. Upon excitation, the complexes undergo rapid triplet-triplet energy transfer (TTET) to the acceptor excited states. This report describes five bis-cyclometalated iridium complexes using two different pyrene-substituted isocyanides with the general formula [Ir(C^N)₂(CNAr)₂]PF₆ (C^N = cyclometalating ligand, CNAr = isocyanide ancillary ligand: CNAr^pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide, CN^pyr = 1-pyrenyl isocyanide). The synthesized complexes were thoroughly characterized via ¹H and ¹³C{¹H} NMR spectroscopy, Fourier-transform Infrared spectroscopy, and electrospray ionization mass spectrometry. The excited states were evaluated with UV-vis absorption, steady-state and time-resolved photoluminescence, and transient absorption spectroscopy. Phosphorescence is completely quenched at room temperature, but in the solvent glass matrix at 77 K, there is luminescence originating from a π → π* triplet state on the pyrene moiety, abbreviated herein as ³pyrene. All five complexes display intense and long-lived ESA originating from the ³pyrene state. The localization of the ground-state absorption on the cyclometalating ligands and the excited-state absorption on the pyrene moiety allows for independent tuning of ground-state absorption (GSA) and ESA to optimize RSA and other NLO attributes.