The emitting triplet state of fac-Ir(ppy)(3) (fac-tris(2-phenylpyridine)iridium) is studied for the first time on the basis of highly resolved optical spectra in the range of the electronic 0-0 transitions. For the compound dissolved in CH(2)Cl(2) and cooled to cryogenic temperatures, three 0-0 transitions corresponding to the triplet substates I, II, and III are identified. They lie at 19,693 cm(-1) (507.79 nm, I → 0), 19,712 cm(-1) (507.31 nm, II → 0), and 19,863 cm(-1) (503.45 nm, III → 0). From the large total zero-field splitting (ZFS) of 170 cm(-1), the assignment of the emitting triplet term as a (3)MLCT state (metal-to-ligand charge transfer state) is substantiated, and it is seen that spin-orbit couplings to higher lying (1,3)MLCT states are very effective. Moreover, the studies provide emission decay times for the three individual substates of τ(I) = 116 μs, τ(II) = 6.4 μs, and τ(III) = 200 ns. Further, group-theoretical considerations and investigations under application of high magnetic fields up to B = 12 T allow us to conclude that all three substates are nondegenerate and that the symmetry of the complex in the CH(2)Cl(2) matrix cage is lower than C(3). It follows that the triplet parent term is of (3)A character. Studies of the emission decay time and photoluminescence quantum yield, Φ(PL), of Ir(ppy)(3) in poly(methylmethacrylate) (PMMA) in the temperature range of 1.5 ≤ T ≤ 370 K reveal average and individual radiative and nonradiative decay rates and quantum yields of the substates. In the range 80 ≤ T ≤ 370 K, Φ(PL) is as high as almost 100%. The quantum yield Φ(PL) drops to ∼88% when cooled to T = 1.5 K. The investigations show further that the emission properties of Ir(ppy)(3) depend distinctly on the complex's environment or the matrix cage according to distinct changes of spin-orbit coupling effectiveness. These issues also have consequences for optimizations of the material's properties if applied as an organic light-emitting diode (OLED) emitter.
A series of highly luminescent dinuclear copper(I) complexes has been synthesized in good yields using a modular ligand system of easily accessible diphenylphosphinopyridine-type P^N ligands. Characterization of these complexes via X-ray crystallographic studies and elemental analysis revealed a dinuclear complex structure with a butterfly-shaped metal-halide core. The complexes feature emission covering the visible spectrum from blue to red together with high quantum yields up to 96%. Density functional theory calculations show that the HOMO consists mainly of orbitals of both the metal core and the bridging halides, while the LUMO resides dominantly on the heterocyclic part of the P^N ligands. Therefore, modification of the heterocyclic moiety of the bridging ligand allows for systematic tuning of the luminescence wavelength. By increasing the aromatic system of the N-heterocycle or through functionalization of the pyridyl moiety, complexes with emission maxima from 481 to 713 nm are obtained. For a representative compound, it is shown that the ambient-temperature emission can be assigned as a thermally activated delayed fluorescence, featuring an attractively short emission decay time of only 6.5 μs at ϕPL = 0.8. It is proposed to apply these compounds for singlet harvesting in OLEDs.
Luminescent materials showing thermally activated delayed fluorescence (TADF) have gained high attractiveness as emitters in organic light emitting diodes (OLEDs) and other photonic applications. Nevertheless, even utilization of TADF can be further improved, introducing a novel concept. This is demonstrated by a new class of brightly luminescent low-cost Cu(I) compounds, for which the emission stems from both the lowest excited triplet T1 and singlet S1 state. At T = 300 K, these materials exhibit quantum yields of more than ΦPL = 90% at short emission decay times. About 80% of the emission intensity stems from the singlet due to TADF, but importantly, an additional 20% is contributed by the lower lying triplet state according to effective spin-orbit coupling (SOC). SOC induces also a relatively large zero-field splitting of the triplet being unusual for Cu(I) complexes. Thus, the overall emission decay time is distinctly reduced. Combined use of both decay paths opens novel photonic applications, in particular, for OLEDs.
The well-known red emitting complex Ir(btp)2(acac) (bis(2-(2'-benzothienyl)-pyridinato-N,C3')iridium(acetylacetonate)), frequently used as emitter material in OLEDs, has been investigated in a polycrystalline CH2Cl2 matrix. The studies were carried out under variation of temperature down to 1.2 K and at magnetic fields up to B=10 T. Highly resolved emission and excitation spectra of several specific sites are obtained by site-selective spectroscopy. For the preferentially investigated site (I-->0 at 16268 cm-1), the three substates I, II, and III of the T1 triplet state are separated by DeltaEII-I=2.9 cm-1 and DeltaEIII-I=25.0 cm-1, respectively. DeltaEIII-I represents the total zero-field splitting (ZFS). The individual decay times of these substates are tauI=150 micros, tauII=58 micros, and tauIII=2 micros, respectively. The long decay time of the lowest substate I indicates its almost pure triplet character. The time for relaxation from state II to state I (spin-lattice relaxation, SLR) is as long as 22 micros at T=1.5 K, while the thermalization between the two lower lying substates and substate III is fast. Application of a magnetic field induces Zeeman mixing of the substates of T1, resulting in an increased splitting between the two lower lying substates from 2.9 cm-1 at zero field to, for example, 6.8 cm-1 at B=10 T. Further, the decay time of the B-field perturbed lowest substate IB decreases by a factor of about 7 up to 10 T. The magnetic field properties clearly show that the three investigated states belong to the same triplet parent term of one single site. Other sites show a similar behavior, though the values of ZFS vary between 15 and 27 cm-1. Since the amount of ZFS reflects the extent of MLCT (metal-to-ligand charge transfer) parentage, it can be concluded that the emitting state T1 is a 3LC (ligand centered) state with significant admixtures of 1,3MLCT (metal-to-ligand charge transfer) character. Interestingly, the results show that the MLCT perturbation is different for the various sites. An empirical correlation between the amount of ZFS and the compound's potential for its use as emitter material in an OLED is presented. As a rule of thumb, a triplet emitter is considered promising for application in OLEDs, if it has a ZFS larger than about 10 cm-1.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.