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Funding: The St Andrews team would like to thank EPSRC (EP/P010482/1) and the Leverhulme Trust (RPG-2016-047) for financial support. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F. R. S.-FNRS) under Grant no. 2.5020.11. Y. O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant no. F.4534.21 (MIS-IMAGINE). Two novel π-extended amine/carbonyl-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters have been designed and synthesized. The two emitters are isomeric, composed of nine fused rings and show green-yellow emission. Sym-DiDiKTa and Asym-DiDiKTa possess tert-butyl groups distributed in a symmetrical and asymmetrical fashion, respectively, which significantly impact the single-crystal packing structure. The two compounds possess similar singlet–triplet energy gaps, ΔEST, of around 0.23 eV, narrowband emission characterized by a full-width at half-maximum, FWHM, of 29 nm and a photoluminescence quantum yield, ΦPL, of 70% and 53% for the symmetric and asymmetric counterparts, respectively, in toluene. Investigation in OLEDs demonstrated that the devices with Sym-DiDiKTa and Asym-DiDiKTa displayed electroluminescence maxima of 543 and 544 nm, and maximum external quantum efficiencies (EQEmax) of 9.8% and 10.5%, respectively. The maximum EQE was further improved to 19.9% by employing a hyperfluorescence strategy. We further present the first example of a neutral MR-TADF emitter incorporated in a LEC device where Sym-DiDiKTa acts as the emitter. The LEC shows a λEL at 551 nm and FWHM of 60 nm with luminance of 300 cd m−2 and a fast turn-on time of less than 2 s to 100 cd m−2. Publisher PDF

AKG is grateful to the Royal Society for Newton International Fellowship NF171163. We acknowledge support from the Engineering and Physical Sciences Research Council of the UK (grants EP/P010482/1 and EP/L017008/1). We are also grateful for financial support from the University of St Andrews Restarting Research and Restarting Interdisciplinary Research Funding Schemes (SARRF and SARIRF) which are funded through the Scottish Funding Council grant reference SFC/AN/08/020. We have designed a highly twisted small TADF emitter PXZ-α-DK based on an a-diketone (α-DK) as a strong acceptor and phenoxazine (PXZ) as a strong donor to obtain red-shifted emission in comparison to the equivalent a-diketone linked to 9,9-dimethyl-9,10-dihydroacridine (DMAC). The PXZ-α-DK shows emission at 586 nm and DMAC-α-DK shows emission at 548 nm in 1,3-bis(N-carbazolyl)benzene (mCP) host at 1.5 wt% doping of the emitter, with short-delayed lifetimes of 6.9 μs for PXZ-α-DK and 7.6 μs for DMAC-α-DK. OLEDs fabricated using these emitters show green electroluminescence at 555 nm for DMAC-α-DK, with a maximum external quantum efficiency, EQEmax, of 6.3%, and orange electroluminescence at 585 nm for PXZ-α-DK, with an EQEmax of 0.8%. We corroborate the optoelectronic properties of these emitters with DFT calculations. Postprint

Authors thank EU Horizon 2020 Grant Agreement No. 812872 (TADFlife) for funding. The St Andrews team acknowledges support from the Engineering and Physical Sciences Research Council of the UK (grant EP/P010482/1). The authors from the University of Parma acknowledge the support from the HPC (High Performance Computing) facility of the University of Parma, Italy. Moreover, authors from University of Parma benefited from the equipment and support of the COMP-HUB Initiative, funded by the “Departments of Excellence” program of the Italian Ministry for Education, University and Research (MIUR, 2018-2022). We present the synthesis, optoelectronic characterization, and a detailed theoretical study of DMAC-py-TRZ, a novel, efficient TADF emitter. This compound is a structural relative of the well-known TADF compound DMAC-TRZ, substituting the bridging phenylene for a pyridyl group. This marginal change has an enormous impact on the structure and hence on the photophysics as the steric interactions between the DMAC donor and the bridge that force DMAC-TRZ into an orthogonal conformation are attenuated and permit DMAC-py-TRZ to adopt a planar and slightly bent structure in the ground state. The large degree of conjugation in the bent DMAC-py-TRZ structure, demonstrated by the strong intensity of the lowest excitation with CT character, is responsible for a large singlet triplet gap, hence hindering TADF of this bent conformer. The computational analysis predicts that emission occurs, however, from a relaxed orthogonal excited-state geometry, as confirmed by the huge Stokes shift observed in non-polar solvents. In this relaxed orthogonal geometry TADF is indeed observed. Emission from the unrelaxed state is recovered in glassy frozen solvents, where the emission band is largely blue-shifted compared with measurements in liquid solvent, and TADF is quenched. In amorphous matrices, structural disorder leads to the coexistence of both conformers, even if, depending on the emitter concentration, dual fluorescence may disappear due to a fast energy transfer from the bent to the orthogonal conformers. We maintain that this efficient energy transfer is responsible for the good efficiency of DMAC-py-TRZ devices, because of the presence in the matrix of a sizable proportion of compounds that adopt the bent structure, favorable to act as the host for the orthogonal TADF conformer of DMAC-py-TRZ. Publisher PDF

Funding: Engineering and Physical Sciences Research Council - EP/P010482/1; Leverhulme Trust - RPG-2016-047; Royal Society - SRF\R1\201089; China Scholarship Council - 201603780001; Horizon 2020 Framework Programme - 838885; Fonds De La Recherche Scientifique - FNRS - 2.5020.11; Fonds De La Recherche Scientifique - FNRS - F.4534.21; Horizon 2020 Framework Programme - 101023743. The use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi-resonance TADF (MR-TADF) emitter, DiKTa-LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green-emitting (λEL = 492 nm) solution-processed OLEDs based on DiKTa-LC showed an EQEmax of 13.6%. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed OLEDs. Publisher PDF

Funding: This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska Curie grant agreement No 838885 (NarrowbandSSL). S.M.S. acknowledges support from the Marie Skłodowska-Curie Individual Fellowship (grant agreement No 838885 NarrowbandSSL). We would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E.Z-C. and I.D.W.S acknowledge support from EPSRC (EP/L017008, EP/P010482/1). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F. R. S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n1117545. Y.O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant n° F.4534.21 (MIS-IMAGINE). G. R. acknowledges a grant from the ‘‘Fonds pour la formation a la Recherche dans l’Industrie et dans l’Agriculture’’ (FRIA) of the FRS-FNRS. We present a p- and n-doped nonacene compound, NOBNacene, that represents a rare example of a linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emitter. This compound shows efficient narrow deep blue emission, with a λPL of 410 nm, full width at half maximum, FWHM, of 38 nm, photoluminescence quantum yield, ΦPL of 71 %, and a delayed lifetime, τd of 1.18 ms in 1.5 wt % TSPO1 thin film. The organic light-emitting diode (OLED) using this compound as the emitter shows a comparable electroluminescence spectrum peaked at 409 nm (FWHM=37 nm) and a maximum external quantum efficiency (EQEmax) of 8.5 % at Commission Internationale de l’Éclairage (CIE) coordinates of (0.173, 0.055). The EQEmax values were increased to 11.2 % at 3 wt % doping of the emitter within the emissive layer of the device. At this concentration, the electroluminescence spectrum broadened slightly, leading to CIE coordinates of (0.176, 0.068). Publisher PDF

Funding: The St Andrews team is grateful to the Engineering and Physical Sciences Research Council (EPSRC) for support from grants EP/P010482/1, EP/R035164/1 and EP/L017008/1. Kyushu team would like to acknowledge Kyulux inc and JSPS Core-to-Core Program (grant number: JPJSCCA20180005) for the support of this project. Three new 1,2,4,5-tetraphenylimidazole derivatives, 9,9-dimethyl-10-(4-(2,4,5-triphenyl-1H-imidazol-1-yl)phenyl)-9,10-dihydroacridine ( DMAC - TPI ), 10-(4-(2,4,5-triphenyl-1H-imidazol-1-yl)phenyl)-10H-phenoxazine ( PXZ-TPI ), and 10-(4-(2,4,5-triphenyl-1H-imidazol-1-yl)phenyl)-10H-phenothiazine ( PTZ - TPI ), bearing different electron donors at the N1 position of the imidazole were synthesised and characterised. DMAC - TPI and PXZ - TPI showed narrow emission at λPL of 388 and 418 nm in toluene, and in doped films in Zeonex polymer (1 wt.%) at λPL 381 and 407 nm, respectively, with a full width at half maximum (FWHM) ranging 0.42-0.44 eV. DMAC - TPI and PXZ - TPI are predicted to show very low oscillator strength for the low-energy transitions, which aligns to the observed low photoluminescence quantum yields. Both molecules showed a singlet-triplet energy gap (ΔEST of around 1.2 eV) that is much too large to enable reverse intersystem crossing and thermally activated delayed fluorescence. Connecting a donor group to TPI at the N1 position can lead to room temperature phosphorescence (RTP), as the example of PTZ - TPI showed. Publisher PDF

We present the synthesis, optoelectronic characterization, and a detailed theoretical study of DMAC-py-TRZ, a novel, efficient TADF emitter. This compound is a structural relative of the well-known TADF compound DMAC-TRZ, substituting the bridging phenylene for a pyridyl group. This marginal change has an enormous impact on the structure and hence on the photophysics as the steric interactions between the DMAC donor and the bridge that force DMAC-TRZ into an orthogonal conformation are attenuated and permit DMAC-py-TRZ to adopt a planar and slightly bent structure in the ground state. The large degree of conjugation in the bent DMAC-py-TRZ structure, demonstrated by the strong intensity of the lowest excitation with CT character, is responsible for a large singlet triplet gap, hence hindering TADF of this bent conformer. The computational analysis predicts that emission occurs, however, from a relaxed orthogonal excited-state geometry, as confirmed by the huge Stokes shift observed in non-polar solvents. In this relaxed orthogonal geometry TADF is indeed observed. Emission from the unrelaxed state is recovered in glassy frozen solvents, where the emission band is largely blue-shifted compared with measurements in liquid solvent, and TADF is quenched. In amorphous matrices, structural disorder leads to the coexistence of both conformers, even if, depending on the emitter concentration, dual fluorescence may disappear due to a fast energy transfer from the bent to the orthogonal conformers. We maintain that this efficient energy transfer is responsible for the good efficiency of DMAC-py-TRZ devices, because of the presence in the matrix of a sizable proportion of compounds that adopt the bent structure, favorable to act as the host for the orthogonal TADF conformer of DMAC-py-TRZ.

Three new 1,2,4,5-tetraphenylimidazole derivatives, 9,9-dimethyl-10-(4-(2,4,5-triphenyl-1H-imidazol-1-yl)phenyl)-9,10-dihydroacridine (DMAC-TPI), 10-(4-(2,4,5-triphenyl-1H-imidazol-1-yl)phenyl)-10H-phenoxazine (PXZ-TPI), and 10-(4-(2,4,5-triphenyl-1H-imidazol-1-yl)phenyl)-10H-phenothiazine (PTZ-TPI), bearing different electron donors at the N1 position of the imidazole were synthesised and characterised. DMAC-TPI and PXZ-TPI showed narrow, deep blue emission at λPL of 388 and 418 nm in toluene, and in doped films in Zeonex polymer (1 wt.%) at λPL 381 and 407 nm, respectively, with a full width at half maximum (FWHM) ranging 0.42-0.44 eV. DMAC-TPI and PXZ-TPI are predicted to show very low oscillator strength for the low-energy transitions, which aligns to the observed low photoluminescence quantum yields. Both molecules showed a singlet-triplet energy gap (EST of around 1.2 eV) that is much too large to enable reverse intersystem crossing and thermally activated delayed fluorescence. Connecting a donor group to TPI at the N1 position can lead to room temperature phosphorescence (RTP), as the example of PTZ-TPI showed.

We present a p- and n-doped nonacene compound, NOBNacene, that represents a rare example of a linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emitter. This compound shows efficient narrow deep blue emission (PL = 410 nm, FWHM = 38 nm, ФPL = 71%, d = 1.18 ms) in 1.5 wt% TSPO1 thin film. The organic light-emitting diode (OLED) using this compound as the emitter shows a comparable electrolumines-cence spectrum (EL = 409 nm, FWHM = 37 nm) and a maximum external quantum efficiency (EQEmax) of 8.5% at CIE coordinates of (0.173, 0.055). The EQEmax values were increased to 11.2% at 3 wt% doping of the emitter within the emissive layer of the device. At this concentra-tion, the electroluminescence spectrum broadened slightly, leading to CIE coordinates of (0.176, 0.068).

We show how borylation of an acceptor-donor-acceptor (A-D-A) thermally activated delayed fluorescence (TADF) emitter, DIDOBNA-N, transforms the compound into a multi-resonant TADF (MR-TADF) emitter, MesB-DIDOBNA-N. DIDOBNA-N emits bright blue light (𝜆PL = 444 nm, FWHM = 64 nm, 𝛷PL = 81%, 𝜏d = 23 𝜇s, 1.5 wt% in TSPO1). The deep blue organic light-emitting diode (OLED) based on this compound shows a very high maximum external quantum efficiency (EQEmax) of 15.3% for a device with CIEy of 0.073. The MR-TADF emitter, MesB-DIDOBNA-N shows efficient and narrowband violet emission (𝜆PL = 402 nm, FWHM = 19 nm, 𝛷PL = 74.7%, 𝜏d = 133 𝜇s, 1.5 wt% in TSPO1). The OLED with MesB-DIDOBNA-N shows out-standing efficiency for a violet OLED at 9.3% and CIEy = 0.044, which is the bluest EL reported for a MR-TADF OLED to date. Noteworthy are the CIE coordinates of (0.166, 0.045), which are very close to the Rec.2020 standard for blue (0.131, 0.046). The EQEmax values were improved from 9.3% to 13.6% by increasing the concentration of the emitter in the host from 1.5 wt% to 5 wt%.

Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which shows thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes are reported. Devices based on 2B-DTACrs showed an EQE

This work was supported financially by the JSPS Core-to-Core Program (grant number: JPJSCCA20180005) and Kyulux Inc. S. M. S. acknowledges support from the Marie Skłodowska-Curie Individual Fellowship (grant agreement No 838885 NarrowbandSSL). We would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E. Z.-C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). We thank the EPRSC for funding (EP/R035164/1). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F. R. S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n1117545. Y. O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant no. F.4534.21 (MIS-IMAGINE). D. B. is a FNRS Research Director. Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which shows thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes are reported. Devices based on 2B-DTACrs showed an EQEmax of 14.8% and CIE coordinates of (0.150, 0.044), which are very close to the BT.2020 requirement for blue pixels. Publisher PDF

We designed and synthesized two new ionic thermally activated delayed fluorescent (TADF) emitters that are charged analogues of a known multiresonant TADF (MR-TADF) compound, DiKTa. The emission of the charged derivatives is red-shifted compared to the parent com-pound. For instance, DiKTa-OBuIm emits in the green (λPL = 499 nm, 1 wt% in mCP) while DiKTa-DPA-OBuIm emits in the red (λPL = 577 nm, 1 wt% in mCP). In 1 wt% mCP films, both emitters showed good photoluminescence quantum yields of 71% and 61%, and delayed life-times of 316.6 μs and 241.7 μs, respectively, for DiKTa-OBuIm and DiKTa-DPA-OBuIm, leading to reverse intersystem crossing rates of 2.85 × 103 s-1 and 3.04 × 103 s-1. Light-emitting electrochemical cells were prepared using both DiKTa-OBuIm and DiKTa-DPA-OBuIm as ac-tive emitters showing green (λmax = 534 nm) and red (λmax = 656 nm) emission, respectively.

Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which showing thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes were designed and synthesized in good yields. Precise control of the extent of borylation was achieved by modulating the reaction temperature and stoichiometry of the Lewis acid in the reaction. A comprehensive structural, theoretical, photophysical, electrochemical, and electroluminescent study is presented. Both emitters possess high photoluminescence quantum yields of up to 83%, small full width at half maximums (FWHMs) of around 24 nm, and deep blue emissions of around 450 nm in mCBP films. Devices based on 2B-DTACrs showed high maximum external quantum effi-ciencies of 14.8% and a deep-blue emission at 447 nm together with Commission Internatio-nale de l’Éclairage coordinates of (0.150, 0.044), which are very close to the BT.2020 re-quirement for blue pixels.

G. P. thanks the SCBM, the “PTC du CEA” (POLEM) and the ANR (iChiralight, ANR-19-CE07-0040) for funding and David Buisson, Amélie Goudet and Sabrina Lebrequier. J. C. and L. Fa. acknowledge the Ministère de l’Education Nationale, de la Recherche et de la Technologie, the CNRS and the Spectroscopies-CDTP core facility is also acknowledged. The St. Andrews team thanks the China Scholarship Council, 201906250199 to W. S. and 202006250026 to J. W., E. Z.-C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). We thank the EPSRC (EP/R035164/1) for funding. We describe herein a molecular design to generate circularly polarized thermally activated delayed fluorescence emitters in which chiral bicarbazole donors are connected to acceptor units via a rigid 8-membered cycle and how the nature of the donor and acceptor units affect the photophysical and chiroptical properties. Publisher PDF

The use of thermally activated delayed fluorescence emitters and emitters that show preferential horizontal orientation of their transition dipole are two emerging strategies to enhance the efficiency of organic light-emitting diodes. We present the first example of a liquid crystalline multi-resonance thermally activated delayed fluorescent emitter, DiKTaLC. The neat film of DiKTaLC shows a photoluminescence quantum yield of 41%, a singlet-triplet energy gap, ΔEST, of 0.20 eV, and a delayed lifetime, τd, of 70.2 µs. The compound possesses a nematic discotic liquid crystalline phase between 80 °C and 110 °C. More importantly, the transition dipole moment of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.26. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed organic light-emitting diodes.

Funding: Scottish Funding Council (SFC/AN/08/020), Leverhulme Trust (RPG-2016-047), H2020 Marie Skłodowska-Curie Actions (838009, 859752), UK Engineering and Physical Sciences Research Council (EP/P010482/1, EP/R00188X/1), Royal Society (SRF\R1\201089), Fonds De La Recherche Scientifique - FNRS (2.5020.11, F.4534.21), Università di Pisa (PRA 2020_21). We present the first example of a multi-resonant thermally activated delayed fluorescent (MR-TADF) extended helicene, Hel-DiDiKTa. This S-shaped double helicene exhibits sky-blue emission, a singlet-triplet energy gap, ΔEST, of 0.15 eV and narrow emission at a peak maximum of 473 nm with a full-width at half-maximum of 44 nm in toluene. The MR-TADF character is confirmed by the small degree of positive solvatochromism and temperature-dependent increase in intensity of the delayed emission. The chiroptical properties of the separated enantiomers are similar to other large helicenes with comparable dissymmetry values, but with the added benefit of MR-TADF. (P)-Hel-DiDiKTa is stable towards enantiomerization, with a Gibbs free energy of activation for enantiomerization (ΔGe‡) of 31± 2 kcal mol-1 at 298 K, a value similar to other reported double helicenes. (P)-Hel-DiDiKTa is also thermally stable, with a 5% weight loss at 399 oC revealed by thermogravimetric analysis (TGA). Thus, this study further strengthens the burgeoning area of chiral TADF emitters for use in cutting-edge optoelectronic and photocatalytic molecules and materials. Publisher PDF