From Mono- to Polynuclear 2-(Diphenylphosphino)pyridine-Based Cu(I) and Ag(I) Complexes: Synthesis, Structural Characterization, and DFT Calculations.

A series of monometallic Ag(I) and Cu(I) halide complexes bearing 2-(diphenylphosphino)pyridine (PyrPhos, L) as a ligand were synthesized and spectroscopically characterized. The structure of most of the derivatives was unambiguously established by X-ray diffraction analysis, revealing the formation of mono-, di-, and tetranuclear complexes having general formulas MXL3 (M = Cu, X = Cl, Br; M = Ag, X = Cl, Br, I), Ag2X2L3 (X = Cl, Br), and Ag4X4L4 (X = Cl, Br, I). The Ag(I) species were compared to the corresponding Cu(I) analogues from a structural point of view. The formation of Cu(I)/Ag(I) heterobimetallic complexes MM'X2L3 (M/M' = Cu, Ag; X = Cl, Br, I) was also investigated. The X-ray structure of the bromo-derivatives revealed the formation of two possible MM'Br2L3 complexes with Cu/Ag ratios, respectively, of 7:1 and 1:7. The ratio between Cu and Ag was studied by scanning electron microscopy-energy-dispersive X-ray analysis (SEM-EDX) measurements. The structure of the binuclear homo- and heterometallic derivatives was investigated using density functional theory (DFT) calculations, revealing the tendency of the PyrPhos ligands not to maintain the bridging motif in the presence of Ag(I) as the metal center.

A Brief History of OLEDs-Emitter Development and Industry Milestones.

Organic light-emitting diodes (OLEDs) have come a long way ever since their first introduction in 1987 at Eastman Kodak. Today, OLEDs are especially valued in the display and lighting industry for their promising features. As one of the research fields that equally inspires and drives development in academia and industry, OLED device technology has continuously evolved over more than 30 years. OLED devices have come forward based on three generations of emitter materials relying on fluorescence (first generation), phosphorescence (second generation), and thermally activated delayed fluorescence (third generation). Furthermore, research in academia and industry toward the fourth generation of OLEDs is in progress. Excerpts from the history of green, orange-red, and blue OLED emitter development on the side of academia and milestones achieved by key players in the industry are included in this report.

Various Structural Design Modifications: para-Substituted Diphenylphosphinopyridine Bridged Cu(I) Complexes in Organic Light-Emitting Diodes.

The well-known system of dinuclear Cu(I) complexes bridged by 2-(diphenylphosphino)pyridine (PyrPhos) derivatives Cu2X2L3 and Cu2X2LP2 (L = bridging ligand, P = ancillary ligand) goes along with endless variation options for tunability. In this work, the influence of substituents and modifications on the phosphine moiety of the NP-bridging ligand was investigated. In previous studies, the location of the lowest unoccupied molecular orbital (LUMO) of the copper complexes of the PyrPhos family was found to be located on the NP-bridging ligand and enabled color tuning in the whole visible spectrum. A multitude of dinuclear Cu(I) complexes based on the triple methylated 2-(bis(4-methylphenyl)phosphino)-4-methylpyridine (Cu-1b-H, Cu-1b-MeO, and Cu-1b-F) up to complexes bearing 2-(bis(4-fluorophenyl)phosphino)pyridine (Cu-6a-H) with electron-withdrawing fluorine atoms over many other variations on the NP-bridging ligands were synthesized. Almost all copper complexes were confirmed via single crystal X-ray diffraction analysis. Besides theoretical TDDFT-studies of the electronic properties and photophysical measurements, the majority of the phosphino-modified Cu(I) complexes was tested in solution-processed organic light-emitting diodes (OLEDs) with different heterostructure variations. The best results of the OLED devices were obtained with copper emitter Cu-1b-H in a stack architecture of ITO/PEDOT-PSS (50 nm)/poly-TPD (15 nm)/20 wt % Cu(I) emitter:CBP:TcTA(7:3) (45 nm)/TPBi (30 nm)/LiF(1 nm)/Al (>100 nm) with a high brightness of 5900 Cd/m2 and a good current efficiency of 3.79 Cd/A.

Investigation of Luminescent Triplet States in Tetranuclear CuI Complexes: Thermochromism and Structural Characterization.

To develop new and flexible CuI containing luminescent substances, we extend our previous investigations on two metal-centered species to four metal-centered complexes. These complexes could be a basis for designing new organic light-emitting diode (OLED) relevant species. Both the synthesis and in-depth spectroscopic analysis, combined with high-level theoretical calculations are presented on a series of tetranuclear CuI complexes with a halide containing Cu4 X4 core (X=iodide, bromide or chloride) and two 2-(diphenylphosphino)pyridine bridging ligands with a methyl group in para (4-Me) or ortho (6-Me) position of the pyridine ring. The structure of the electronic ground state is characterized by X-ray diffraction, NMR, and IR spectroscopy with the support of theoretical calculations. In contrast to the para system, the complexes with ortho-substituted bridging ligands show a remarkable and reversible temperature-dependent dual phosphorescence. Here, we combine for the first time the luminescence thermochromism with time-resolved FTIR spectroscopy. Thus, we receive experimental data on the structures of the two triplet states involved in the luminescence thermochromism. The transient IR spectra of the underlying triplet metal/halide-to-ligand charge transfer (3 M/XLCT) and cluster-centered (3 CC) states were obtained and interpreted by comparison with calculated vibrational spectra. The systematic and significant dependence of the bridging halides was analyzed.

Real-time observation of molecular flattening and intersystem crossing in [(DPEPhos)Cu(i)(PyrTet)] via ultrafast UV/Vis- and mid-IR spectroscopy on solution and solid samples.

The primary photo-induced processes in the mononuclear, heteroleptic Cu(i) complex [(DPEPhos)Cu(PyrTet)] (1), relevant for OLED applications, were investigated in various solvents and in solid state samples via femtosecond (fs) time resolved UV/Vis and fs time resolved mid-IR transient absorption spectroscopy (TA) with MLCT excitation around 340 nm. UV/Vis fs-TA on 1 in solution reveals (i) a severe blue-shift of excited state absorption on the time scale of a few picoseconds (τ2) that is not observed in solids, and (ii), on the time scale of several tens of picoseconds (τ3), a process with very similar dynamics in all samples. Mid-IR fs-TA in solution indicates structural changes with τ2. Transient absorption anisotropy experiments temporally resolve a viscosity-dependent change of the excited state transition dipole moment orientation with τ2, as quantitatively predicted for the relaxed S1-state via TD-DFT. The results strongly suggest flattening distortion (FD) and structural rearrangement of the PyrTet-moiety to occur on the time scale of τ2 in liquid phase, and to be suppressed in solid phase. Moreover, intersystem crossing (ISC) is assigned to the process described by τ3, in line with its direct observation via time-resolved luminescence spectroscopy on 1 by Bergmann et al. (Sci. Adv., 2016, 2, e1500889). Overall, the use of structure-sensitive methods and the direct comparison of different preparations of 1 (i.e. solution vs. solid state), are a unique basis for a clear assignment of spectro-temporal characteristics to fundamental deactivation processes such as FD and ISC.

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes.

Luminescent Cu(i) AlkylPyrPhos complexes with a butterfly-shaped Cu2I2 core and halogen containing ancillary ligands, with a special focus on fluorine, have been investigated in this study. These complexes show extremely high solubilities and a remarkable (photo)chemical stability in a series of solvents. A tunable emission resulting from thermally activated delayed fluorescence with high quantum yields was determined by luminescence and lifetime investigations in solvents and solids. Structures of the electronic ground states were analyzed by single crystal X-ray analysis. The structure of the lowest excited triplet state was determined by transient FTIR spectroscopy, in combination with quantum chemical calculations. With the obtained range of compounds we address the key requirement for the production of organic light emitting diodes based on solution processing.