Highly Efficient Photo- and Electroluminescence from Two-Coordinate Cu(I) Complexes Featuring Nonconventional N-Heterocyclic Carbenes.

A series of six luminescent two-coordinate Cu(I) complexes were investigated bearing nonconventional N-heterocyclic carbene ligands, monoamido-aminocarbene (MAC*) and diamidocarbene (DAC*), along with carbazolyl (Cz) as well as mono- and dicyano-substituted Cz derivatives. The emission color can be systematically varied over 270 nm, from violet to red, through proper choice of the acceptor (carbene) and donor (carbazolyl) groups. The compounds exhibit photoluminescent quantum efficiencies up to 100% in fluid solution and polystyrene films with short decay lifetimes (τ ≈ 1 µs). The radiative rate constants for the Cu(I) complexes ( kr = 105-106 s-1) are comparable to state of the art phosphorescent emitters with noble metals such as Ir and Pt. All complexes show strong solvatochromism due to the large dipole moment of the ground states and the transition dipole moment that is in the opposite direction. Temperature-dependent studies of (MAC*)Cu(Cz) reveal a small energy separation between the lowest singlet and triplet states (Δ ES1-T1 = 500 cm-1) and an exceptionally large zero-field splitting (ZFS = 85 cm-1). Organic light-emitting diodes (OLEDs) fabricated with (MAC*)Cu(Cz) as a green emissive dopant have high external quantum efficiencies (EQE = 19.4%) and brightness of 54 000 cd/m2 with modest roll-off at high currents. The complex can also serve as a neat emissive layer to make highly efficient OLEDs (EQE = 16.3%).

Rapid Multiscale Computational Screening for OLED Host Materials.

The design of new host materials for phosphorescent organic light emitting diodes (OLEDs) is challenging because several physical property requirements must be met simultaneously. A triplet energy ( ET) higher than that of the chosen emitting dopant, appropriate highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels, good charge carrier transport, and high stability are all required. Here, computational methods were used to screen structures to find the most promising candidates for OLED hosts. The screening was carried out in three Tiers. The Tier 1 selection, based on density functional theory calculations, identified a set of eight molecular structures with ET > 2.9 eV, suitable for hosting blue phosphorescent dopants such as iridium(III)bis((4,6-di-fluorophenyl)-pyridinato-N,C2')picolinate. Phenanthro[9,10- d]imidazole was chosen as the starting point for the Tier 2 selection. Thirty-seven unique molecular structures were enumerated by isoelectronic nitrogen transmutation of up to two CH fragments of the phenanthrene. Three molecules, that is, imidazo[4,5- f]-phenanthrolines with nitrogens at the 1,10-, 3,8-, and 4,7-positions, were selected for Tier 3, which involved the use of molecular dynamics simulations and electron coupling calculations to predict differences in charge transport between the three materials. The three were explored experimentally through synthesis and device fabrication. The singlet, triplet, and frontier orbital energies computed using single-molecule density functional theory calculations ( Tiers 1 and 2) were consistent with the experimental values in a fluid solution, and the multiscale modeling scheme ( Tier 3) correctly predicted the poor device performance of one material. We conclude that screening host materials using only single-molecule quantum mechanical data was not sufficient to predict whether a given material would make a good OLED host with certainty; however, they can be used to screen out materials that are destined to fail due to low singlet/triplet energies or a poor match of the frontier orbital energies to the dopant or transport materials.

Boron Dipyridylmethene (DIPYR) Dyes: Shedding Light on Pyridine-Based Chromophores.

Boron dipyrromethene (BODIPY) derivatives have found widespread utility as chromophores in fluorescent applications, but little is known about the photophysical properties of pyridine-based BODIPY analogues, dipyridylmethene dyes. Indeed, it has been reported that boron difluoride dipyridylmethene (DIPYR) is nonemissive, and that derivatives of DIPYR have modest, if any, luminescence. In this report, we explore this little-touched area of chemical space and investigate the photophysical properties of three simple DIPYR dyes: boron dipyridylmethene, boron diquinolylmethene, and boron diisoquinolylmethene. The three dyes strongly absorb in the blue-green part of the spectrum (λem = 450-520 nm, ε = 2.9-11 × 104 M-1 cm-1) and display green fluorescence with high quantum yields (ΦPL = 0.2, 0.8, and 0.8, respectively). Key photophysical properties in these systems were evaluated using a combination of TD-DFT and extended multiconfigurational quasidegenerate second-order perturbation theory (XMCQDPT2) methods and compared to experimental results, revealing that high quantum yields of the quinoline and isoquinoline derivatives are a result of the relative reordering of S1 and T2 state energies upon benzannulation of the parent structure. The intense absorption and high emission efficiency of the benzannulated derivatives make these compounds an intriguing class of dyes for further derivatization.