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Authors are grateful to the Engineering and Physical Sciences Research Council (EPSRC) for support from grants EP/P010482/1 and EP/R035164/1. P. Rajamalli acknowledges support from a Marie Skłodowska-Curie Individual Fellowship (MCIF; No. 749557). Dongyang Chen thanks the China Scholarship Council (grant numbers 201603780001). We present a study of two isomeric thermally activated delayed fluorescence (TADF) emitters 9,9'- (sulfonylbis(pyrimidine-5,2-diyl))bis(3,6-di-tert-butyl-9H-carbazole) ( pDTCz-DPmS ) and 9,9'- (sulfonylbis(pyrazine-5,2-diyl))bis(3,6-di-tert-butyl-9H-carbazole) ( pDTCz-DPzS ). The use of pyrimidine and pyrazine as bridging units between the electron donor and acceptor moieties is found to be advantageous compared to the phenyl- (pDTCz-DPS) and pyridine-based analogues ( pDTCz-3DPyS and pDTCz-2DPyS ). Conformational modulation of the donor groups as a function of the bridge results in high photoluminescence quantum yields (ΦPL > 68%) and small energy gaps between singlet and triplet excited states (ΔEST < 160 meV). OLEDs using pDTCz-DPmS and pDTCz-DPzS as emitters exhibit blue and green electroluminescence, respectively, with higher maximum external quantum efficiencies (EQEmax of 14% and 18%, respectively) and reduced efficiency roll-off as compared to the reference devices using pDTCz-DPS , pDTCz-3DPyS , and pDTCz-2DPyS as the emitters. Our results provide a more complete understanding on the impact of the bridge structure in D-A-D TADF systems on the optoelectronic properties of the emitter, and how the balance between color purity and EQE in the devices can be controlled, advancing the design strategies for TADF emitters. Postprint

Two new asymetric D–A–D′ type compounds containing benzophenone and diphenylsulfone as electron accepting core, and acridan and thianthrene as electron donating moieties were design as multifunctional materials. The influence of different acceptor and donor units on thermally activated delayed fluorescence and room temperature phosphorescence was investigated and discussed. The combination of different donors with benzophenone unit resulted in the compound with effective frontier orbital separation, as well as the sustainment of high radiative rate. These statements are both experimentally and theoretically supported using time-resolved photoluminescence spectroscopy and DFT calculations. Deoxygenation experiment revealed higher triplet exciton contribution in the emission of benzophenone derivative, as compared to that of diphenylsulfone-based compound. The films of molecular mixtures of these emitters with 1,3-bis(N-carbazolyl)benzene demonstrated temperature-dependent photoluminescence. The estimated energy gaps between the lowest singlet and triplet states were found to be 0.06 eV and 0.27 eV for benzophenone and diphenylsulfone derivatives, respectively. Due to the relatively high singlet-triplet energy splitting of the diphenylsulfone-based compound, triplet harvesting was detected not only via temperature-stimulated fluorescence but also via room temperature phosphorescence. Displaying effect of triplet harvesting on efficiency of all-organic blue and green OLEDs based on thianthrene and acridan-substituted benzophenone or diphenylsulfone derivatives demonstrated very different maximum external quantum efficiencies of 1.4 and 22.2% respectively.

Excited state dynamics of trinary star-shaped dendritic compounds with triphenylamine arms and different cores were studied by means of time-resolved fluorescence and transient absorption. Under optical excitation, nonpolar C3 symmetry molecules form polar excited states localized on one of the molecular substituents. Conformational excited state stabilization of molecules with an electron-accepting core causes a formation of twisted internal charge transfer (TICT) states in polar solvents. A low transition dipole moment from TICT state to the ground state causes very weak fluorescence of those compounds and strong dependence on the solvent polarity. The compound formed from the triphenylamine central core and identical arms also experiences excited state twisting, however, weakly sensitive to the solvent polarity.

Elaboration of the appropriate host materials proved to be not less important for the fabrication of a highly efficient OLED than the design of emitters. In the present work, we show how by simple variation of molecular structure both blue emitters exhibiting delayed fluorescence and ambipolar high triplet energy hosts can be obtained. The compounds with a para-junction revealed higher thermal stability (TID up to 480 °C), lower ionization potentials (5.51–5.60 eV), exclusively hole transport, and higher photoluminescence quantum efficiencies (0.90–0.97). Meta-linkage leads to ambipolar charge transport and higher triplet energies (2.82 eV). Introduction of the accepting nitrile groups in the para-position induces intensive delayed fluorescence via a triplet–triplet annihilation up-conversion mechanism. By utilization of the para-substituted derivative as an emitter and the meta-substituted isomer as the host, a deep-blue OLED with the external quantum efficiency of 14.1% was fabricated.

In this work, we report on the synthesis and photophysical investigation of a new star-shaped triazine-carbazole derivative 2,4,6-tris(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)-1,3,5-triazine. Comparative study of the photophysical properties of the newly synthesized emitter along with its para-substituted isomer 2,4,6-tris(4-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)-1,3,5-triazine was performed. While para-linkage caused higher oscillator strength of the lowest energy absorption band and high fluorescence quantum yield, the meta-linkage resulted in stronger charge transfer character as well as higher triplet energy. Delayed emission of meta-isomer was found to be 3 orders of magnitude more intense than that of para-isomer. Temperature dependent measurements of meta-isomer confirmed the thermally activated delayed fluorescence origin of its delayed fluorescence with the activation energy of 0.07 eV. Organic light emitting diode containing this emitter dispersed in bis[2-(diphenylphosphino)phenyl] et...

Despite the commercial success of organic emitters based on thermally activated delayed fluorescence (TADF), a general understanding of emitter-matrix interactions is still lacking. How does the dielectric constant around an emitter impact its delayed fluorescence? The authors study the photophysical properties of three emitters in solution, showing that a higher excited triplet state at low dielectric constants can boost the efficiency of blue TADF emitters. Experiments are supported by state-of-the-art quantum simulations. The findings may be generalized to solid-state systems, pointing to tuning of host-guest architectures to improve the efficiency of TADF-based blue OLEDs.

Fluorine-containing donor molecules TFTF, CNTF and PRTF are designed and isomer selectively synthesized for application in vacuum-deposited organic solar cells. These molecules comprise a donor acceptor molecular architecture incorporating thiophene and benzothiadiazole derivatives as the electron-donating and electron-withdrawing moieties, respectively. As opposed to previously reported materials from this class, PRTF can be purified by vacuum sublimation at moderate to high yields because of its higher volatility and better stabilization due to a stronger intramolecular hydrogen bond, as compared to TFTF and CNTF. The UV-vis absorption spectra of the three donors show an intense broadband absorption between 500 nm and 800 nm with, similar positions of their frontier energy levels. The photophysical properties of the three donor molecules are thoroughly tested and optimized in bulk heterojunction solar cells with C-60 as acceptor. PRTF shows the best performance, yielding power conversion efficiencies of up to 3.8%. Moreover, the voltage loss for the PRTF device due to the non radiative recombination of free charge carriers is exceptionally low (0.26 V) as compared to typical values for organic solar cells (>0.34V). (C) 2016 Published by Elsevier B.V.

Three new bipolar star-shaped derivatives of 2,4,6-triphenyl-1,3,5-triazine containing carbazolyl groups were designed, synthesized and characterized. All the materials possess high thermal stability and high glass transition temperatures ranging 97–226 °C. Photophysical study of the dilute solutions and neat films of the synthesized compounds was performed. Lippert–Mataga plots revealed linear dependence of Stokes shifts on the orientation polarizability for all the compounds. The dilute solutions of the triazine derivatives exhibited high photoluminescence quantum yields reaching 0.85, while for the neat films photoluminescence efficiency of 0.20–0.33 was observed. Ionization potentials of the solid layers of carbazole-triazine adducts estimated by photoelectron spectroscopy were found to be in the range of 5.49–5.97 eV. Hole drift mobility of the materials well exceeded the magnitude of 10−3 cm2 V−1 s−1 at an electric field of 6.4 · 105 V/cm. The selected compounds were tested as light emitting materials in organic light emitting diodes based on host-guest systems.

Materials with high triplet energies have attracted great attention for their application in exciplex-based or thermally activated delayed fluorescence-based organic light-emitting diodes. To study the correlation between triplet energy and chemical structure, six compounds with typical donor-acceptor-donor structures were designed, synthesized, and characterized. Through the adjustment of molecular configuration by weakening the strengths of donors and increasing the angles between donors and acceptors, the triplet energies of the materials were gradually increased from 2.5 to 3.0 eV. Three exciplex-based organic light-emitting diodes containing one of the synthesized compounds were fabricated, which exhibited efficient blue, green-yellow, and white thermally activated delayed fluorescence. Blue and green-yellow organic light-emitting diodes exhibited the maximum external quantum efficiencies of 9.1% and 8.3%, respectively. White organic light-emitting diodes showed turn-on voltage of 4.8 V, high maximum luminance of 18474 cdm-2, and maximum external quantum efficiency of 10.6%. Maximum external quantum efficiencies of blue and white organic light-emitting diodes were close to the record values observed for all-exciplex-based blue and white organic light-emitting diodes.

Triazine derived organic materials possessing various donor-chromophores at the periphery have been designed, synthesized and characterized. The synthesized compounds formed molecular glasses. Their glass transition temperatures ranged from 148 to 235 °C. The compounds demonstrated high thermal stability. The onset temperatures of their thermal decomposition exceeded 390 °C. The fluorenyl- and carbazolyl-substituted triazine derivatives were shown to be highly fluorescent in solutions and rigid polymer matrices with fluorescence quantum yields being in the range of 0.73–0.82. The phenothiazinyl-substituted triazine derivative showed moderate fluorescence quantum yields in dilute solution ( η = 0.25) or polymer matrix ( η = 0.50). Photophysical studies of phenothiazinyl-substituted triazine derivative in media of different rigidity and polarity revealed its twisted intramolecular charge transfer character. Neat films of the triazine compounds displayed significant fluorescence quenching accompanied by a non-exponential excited-state decay profile which was attributed to migration-assisted exciton quenching at non-radiative decay sites in disordered media. Differential pulse voltammetry studies of the synthesized materials showed that the nature of donor-substituents attached to the triazine core can influence their redox behaviour. Investigation by cyclic voltammetry revealed that the synthesized materials can be used as monomers to prepare high dimensional conjugated polymers by electro-oxidation. Spectroelectrochemical investigation of electro-oxidation products suggested the formation of charged species like polarons or bipolarons.

Authors thank EU Horizon 2020 Grant Agreement No. 812872 (TADFlife) for funding this project. Further support was obtained by the Helmholtz Association Program at the Karlsruhe Institute of Technology (KIT). The German Research Foundation (formally Deutsche Forschungsgemeinschaft DFG) in the framework of SFB1176 Cooperative Research Centre "Molecular Structuring of Soft Matter" (CRC1176, A4, B3, C2, C6) and the cluster 3D Matter Made To Order all funded under Germany’s Excellence Strategy 2082/1--390761711 are greatly acknowledged for financial contributions. We acknowledge support from the Engineering and Physical Sciences Research Council of the UK (grant EP/P010482/1), from the International Collaborative Research Program of Institute for Chemical Research, Kyoto University (grant # 2020-37 and 2021-37), and from JSPS KAKENHI Grant Number JP20H05840 (Grant-in-Aid for Transformative Research Areas, “Dynamic Exciton”). ZZ acknowledges the financial support from the China Scholarship Council (CSC, 201606890009) for his PhD studies. EZ-C is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). In this work we showcase the emitter DICzTRZ in which we employed a twin-emitter design of our previously reported material, ICzTRZ . This new system presented a redshifted emission at 488 nm compared to that of ICzTRZ at 475 nm and showed a comparable photoluminescence quantum yield of 57.1% in a 20 wt% CzSi film versus 63.3% for ICzTRZ . The emitter was then incorporated within a solution-processed organic light-emitting diode that showed a maximum external quantum efficiency of 8.4%, with Commission Internationale de l’Éclairage coordinate of (0.22, 0.47), at 1 mA cm−2. Publisher PDF

NAK, HFH, MKE, and APM acknowledge the EU’s Horizon 2020 for funding the PHEBE project under grant no. 641725. NAK, MKE, AD, NH and APM acknowledge the EU’s Horizon 2020 for funding the HyperOLED project under grant no. 641725. APM thanks EPSRC grant EP/L02621X/1 for funding. ANB acknowledges an EPSRC Doctoral Training Grant. We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor–acceptor dihedral angles. An unexpected intramolecular dipole interaction imparts a unique molecular geometry to the ortho-linked isomer, while comparison of the meta- and para-isomers uncovers how positional differences in acceptor strengths (a consequence of differences in aromatic π-system electron density) lead to very different triplet harvesting and emission properties. These positional-isomer effects on TADF follow the well-known aromatic directing rules from organic synthesis, in keeping with their common origin arising from contributions of multiple electronic resonance structures. Understanding these positional effects and methods of dihedral control is critical to the future design of efficient TADF emitters. Publisher PDF