Tuning Emission Lifetimes of Ir(C^N) 2 (acac) Complexes with Oligo(phenyleneethynylene) Groups.

Emissive compounds with long emission lifetimes (μs to ms) in the visible region are of interest for a range of applications, from oxygen sensing to cellular imaging. The emission behavior of Ir(ppy) 2 (acac) complexes (where ppy is the 2-phenylpyridyl chelate and acac is the acetylacetonate chelate) with an oligo( para -phenyleneethynylene) (OPE3) motif containing three para-rings and two ethynyl bridges attached to acac or ppy is examined here due to the accessibility of the long-lived OPE3 triplet states. Nine Ir(ppy) 2 (acac) complexes with OPE3 units are synthesized where the OPE3 motif is at the acac moiety (aOPE3), incorporated in the ppy chelate (pOPE3) or attached to ppy via a durylene link (dOPE3). The aOPE3 and dOPE3 complexes contain OPE3 units that are decoupled from the Ir(ppy) 2 (acac) core by adopting perpendicular ring-ring orientations, whereas the pOPE3 complexes have OPE3 integrated into the ppy ligand to maximize electronic coupling with the Ir(ppy) 2 (acac) core. While the conjugated pOPE3 complexes show emission lifetimes of 0.69-32.8 μs similar to the lifetimes of 1.00-23.1 μs for the non-OPE3 Ir(ppy) 2 (acac) complexes synthesized here, the decoupled aOPE3 and dOPE3 complexes reveal long emission lifetimes of 50-625 μs. The long lifetimes found in aOPE3 and dOPE3 complexes are due to intramolecular reversible electronic energy transfer (REET) where the long-lived triplet-state metal to ligand charge transfer ( 3 MLCT) states exchange via REET with the even longer-lived triplet-state localized OPE3 states. The proposed REET process is supported by changes observed in excitation wavelength-dependent and time-dependent emission spectra from aOPE3 and dOPE3 complexes, whereas emission spectra from pOPE3 complexes remain independent of the excitation wavelength and time due to the well-established 3 MLCT states of many Ir(ppy) 2 (acac) complexes. The long lifetimes, visible emission maxima (524-526 nm), and photoluminescent quantum yields of 0.44-0.60 for the dOPE3 complexes indicate the possibility of utilizing such compounds in oxygen-sensing and cellular imaging applications.