1,3,5-Triazine-functionalized thermally activated delayed fluorescence emitters for organic light-emitting diodes

D.S acknowledges support from the Royal Academy of Engineering Enterprise Fellowship (EF2122-13106). This project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Skłødowska-Curie grant agreements No. 897098 (AIE-RTP-PLED). T.W. acknowledges support from the Marie Skłodowska-Curie Individual Fellowship. C.S. acknowledges support from the China Scholarship Council (201806890001). The authors thank the EPSRC (EP/P010482/1) for financial support.The 1,3,5-triazine electron acceptor has become one of the most popular building blocks for the design of thermally activated delayed fluorescence (TADF) materials. Many TADF design strategies are first applied in compounds that contain triazines, and there are numerous examples of organic light-emitting diodes (OLEDs) with triazine-containing emitters that show high efficiencies and long operating lifetimes. A comprehensive review of triazine-containing TADF emitters is provided. This review is organized according to the triazine-derived structural motifs, such as number and position of electron-donor groups in donor?acceptor-type emitters, the π-bridging linkers employed, orientation control of the transition dipole moment, and the design of chiral and through-space charge-transfer emitters. The structure of the compounds with their optoelectronic properties and the corresponding performance of the OLED devices is correlated.Publisher PDFPeer reviewe

The influence of nitrogen doping of the acceptor in orange–red thermally activated delayed fluorescence emitters and OLEDs

Funding: C. Si thanks the China Scholarship Council (201806890001). D.S acknowledges support from the Royal Academy of Engineering Enterprise Fellowship (EF2122-13106). The St Andrews team thanks EPSRC for financial support (EP/P010482/1). X.-H. Zhang acknowledges support from the National Natural Science Foundation of China (Grant Nos. 52130304, 51821002), Suzhou Key Laboratory of Functional Nano & Soft Materials, Collaborative Innovation Center of Suzhou Nano Science & Technology, the 111 Project.Nitrogen-containing polycyclic aromatic hydrocarbons (N-PAH) have been widely used as deep lowest unoccupied molecular orbital (LUMO) acceptors in donor-acceptor (D-A) red thermally activated delayed fluorescent (TADF) emitters and their use in organic light-emitting diodes. However, most of the studies have focused disparately on donor/acceptor combinations to yield efficient emitters, while it is rare that there is a methodological study to investigate the influence of the nitrogen (N) doping ratios on the ground and excited states of PAH acceptors. Here, we report a family of four different N-PAH acceptors containing different numbers of nitrogen atoms within the N-PAH and their use in D-A TADF emitters, DMACBP, DMACPyBP, DMACBPN and DMACPyBPN, when coupled to the same donor, 9,9-dimethyl-9,10-dihydroacridine (DMAC). As the nitrogen content in the acceptor increases the LUMO becomes progressively more stabilized while the singlet-triplet energy gap (ΔEST) decreases and the rate constant for reverse intersystem crossing (kRISC) increases. In particular, introducing nitrogen at the 10-position of the dibenzo[a,c]phenazine (BP) leads to a more than ten-fold enhancement in kRISC in DMACPyBP and DMACPyBPN compared to DMACBP and DMACBPN. Among the OLEDs with all four emitters that with DMACBPN demonstrates the highest EQEmax of 19.4% at an emission peak of 588 nm. while the deepest red emitting device employed DMACPyBPN (λEL = 640 nm) with an EQEmax of 5.4%.Publisher PDFPeer reviewe

Brominated B1-polycyclic aromatic hydrocarbons for the synthesis of deep-red to near-infrared delayed fluorescence emitters

This project has received funding from the Leverhulme Trust (Grant RPG-2022-032) and the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant Agreement 769599). C.S. thanks the China Scholarship Council (201806890001), and M.I. and E.Z.-C. thank the EPSRC Programme Grant “Boron: Beyond the Reagent” (EP/W007517) for support.Bromo-functionalized B1-polycyclic aromatic hydrocarbons (PAHs) with LUMOs of less than −3.0 eV were synthesized and used in cross-couplings to form donor–acceptor materials. These materials spanned a range of S1 energies, with a number showing thermally activated delayed fluorescence and significant emission in the near-infrared region of the spectrum. These B1-PAHs represent a useful family of acceptors that can be readily synthesized and functionalized.Publisher PDFPeer reviewe

Rational molecular design of efficient yellow-red dendrimer TADF for solution-processed OLEDs : a combined effect of substitution position and strength of the donors

Funding: Changfeng Si thanks the China Scholarship Council (201806890001). Dianming Sun acknowledges support from the Royal Academy of Engineering Enterprise Fellowship (EF2122-13106). We thank EPSRC (EP/W015137/1, EP/W524505/1) for financial support. Open Access funding enabled and organized by Projekt DEAL.The development of high-performance solution-processed red organic light-emitting diodes (OLEDs) remains a challenge, particularly in terms of maintaining efficiency at high luminance. Here, we designed and synthesized four novel orange-red thermally activated delayed fluorescence (TADF) dendrimers that are solution-processable: 2GCzBP , 2DPACzBP , 2FBP2GCz and 2FBP2DPACz . We systematically investigated the effect of substitution position and strength of donors on the optoelectronic properties. The reverse intersystem crossing rate constant (kRISC) of the emitters having donors substituted at positions 11 and 12 of the dibenzo[a,c]phenazine (BP) is more than 10-times faster than that of compounds substituted having donors substituted at positions 3 and 6. Compound 2DPACzBP , containing stronger donors than 2GCzBP , exhibits a red-shifted emission and smaller singlet-triplet energy splitting, ΔEST, of 0.01 eV. The solution-processed OLED with 10 wt% 2DPACzBP doped in mCP emitted at 640 nm and showed a maximum external quantum efficiency (EQEmax) of 7.8%, which was effectively maintained out to a luminance of 1,000 cd m−2. Such a device∙s performance at relevant display luminance is among the highest for solution-processed red TADF OLEDs. The efficiency of the devices was improved significantly by using 4CzIPN as an assistant dopant in a hyperfluorescence (HF) configuration, where the 2DPACzBP HF device shows an EQEmax of 20.0% at λEL of 605 nm and remains high at 11.8% at a luminance of 1,000 cd m−2, which makes this device one of the highest efficiency orange-to-red HF SP-OLEDs to date.Peer reviewe

Fluorinated dibenzo[a,c]-phenazine-based green to red thermally activated delayed fluorescent OLED emitters

Purely organic thermally activated delayed fluorescence (TADF) emitting materiaLs for organic Light-emitting diodes (OLEDs) enable a facile method to modulate the emission color through judicious choice of donor and acceptor units. Amongst purely organic TADF emitters, the development of TADF molecules that emit at Longer wavelengths and produce high-efficiency devices that show Low efficiency roll-off remains a challenge. We report a modular synthesis route that delivers three structurally related fluorinated dibenzo[a,c]-phenazine-based TADF molecules, each bearing two donor moieties with different electron-donating strengths, namely 3,6-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-10-fluorodi-benzo[a,c]phenazine (2DTCz-BP-F), 3,6- bis(9,9-dimethylacridin-10(9H)-yl)-10-fluorodibenzo[a,c]-phenazine (2DMAC-BP-F) and 10,10'-(10-fluorodibenzo[a,c]phenazine-3,6-diyl)bis(10H-phenoxazine) (2PXZ-BP-F). They exhibit donor strength-controlled color-tuning over a wide color range from green to deep-red with photoluminescence maxima, lambda(PL), of 505 nm, 589 nm, and 674 nm in toluene solution. OLED devices using these TADF materials showed excellent to moderate performance with an EQE(max) of 21.8% in the case of 2DMAC-BP-F, 12.4% for 2PXZ-BP-F and 2.1% with 2DTCZ-BP-F, and associated electroluminescence (EL) emission maxima, lambda(EL), of 585 nm, 605 nm and 518 nm in an mCBP host, respectively.Peer reviewe

The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies

The research leading to these results has received funding from the European Research Council under the Horizon 2020 Research and Innovation Program (Grant no. 769599), the Leverhulme Trust (RPG-2014-340) and the EPSRC (EP/P010482/1). C. Si thanks the China Scholarship Council (201806890001).The synthesis of a range of brominated-Bn-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr3 with appropriately substituted alkynes via a bromoboration/electrophilic C-H borylation sequence. The brominated-Bn-PAHs were isolated as either the borinic acid or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B2-doped PAHs (with one example having a reduction potential of E1/2 = -0.96 V versus Fc+/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters direct from internal alkynes. Bromoboration/C-H borylation installs useful C-Br units onto the Bn-PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B2-PAH. The resultant D-A-D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.Publisher PDFPeer reviewe

Multi-responsive thermally activated delayed fluorescence materials : optical ZnCl2 sensors and efficient green to deep-red OLEDs

Funding: China Scholarship Council - 201806890001; Engineering and Physical Sciences Research Council - EP/L017008/1; Horizon 2020 Framework Programme - 101024874; Royal Society - NF171163.Thermally activated delayed fluorescence (TADF) is an emission mechanism whereby both singlet and triplet excitons can be harvested to produce light. Significant attention is devoted to developing TADF materials for organic light-emitting diodes (OLEDs), while their use in other organic electronics applications such as sensors, has lagged. A family of TADF emitters, TPAPyAP, TPAPyBP, and TPAPyBPN containing a triphenylamine (TPA) donor and differing nitrogen-containing heterocyclic pyrazine-based acceptors is developed and systematically studied. Depending on the acceptor strength, these three compounds emit with photoluminescence maxima (λPL), of 516, 550, and 575 nm in toluene. Notably, all three compounds show a strong and selective spectral response to the presence of ZnCl2, making them the first optical TADF sensors for this analyte. It is demonstrated that these three emitters can be used in vacuum-deposited OLEDs, which show moderate efficiencies. Of note, the device with TPAPyBPN in 2,8-bis(diphenyl-phoshporyl)-dibenzo[b,d]thiophene (PPT) host emits at 657 nm and shows a maximum external quantum efficiency (EQEmax) of 12.5%. This electroluminescence is significantly red-shifted yet shows comparable efficiency compared to a device fabricated in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) host (λEL = 596 nm, EQEmax = 13.6%).Peer reviewe

A deep-blue-emitting heteroatom-doped MR-TADF nonacene for high-performance organic light-emitting diodes

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 PDFPeer reviewe

Organic long persistent luminescence from a thermally activated delayed fluorescence compound

Funding: UK EPSRC (grants EP/ P010482/1, EP/J01771X, EP/J00916, and EP/R035164/1). We gratefully acknowledge funding through the EPSRC NSFCBET lead agency agreement (EP/R010595/1,1706207) and a Leverhulme Trust Research Grant (RPG-2017-231).Organic long‐persistent luminescence (OLPL) is one of the most promising methods for long‐lived‐emission applications. However, present room‐temperature OLPL emitters are mainly based on a bimolecular exciplex system which usually needs an expensive small molecule such as 2,8‐bis(diphenyl‐phosphoryl)dibenzo[b,d]thiophene (PPT) as the acceptor. In this study, a new thermally activated delayed fluorescence (TADF) compound, 3‐(4‐(9H‐carbazol‐9‐yl)phenyl)acenaphtho[1,2‐b]pyrazine‐8,9‐dicarbonitrile (CzPhAP), is designed, which also shows OLPL in many well‐known hosts such as PPT, 2,2′,2″‐(1,3,5‐benzinetriyl)‐tris(1‐phenyl‐1‐H‐benzimidazole) (TPBi), and poly(methyl methacrylate) (PMMA), without any exciplex formation, and its OLPL duration reaches more than 1 h at room temperature. Combining the low cost of PMMA manufacture and flexible designs of TADF molecules, pure organic, large‐scale, color tunable, and low‐cost room‐temperature OLPL applications become possible. Moreover, it is found that the onset of the 77 K afterglow spectra from a TADF‐emitter‐doped film is not necessarily reliable for determining the lowest triplet state energy level. This is because in some TADF‐emitter‐doped films, optical excitation can generate charges (electron and holes) that can later recombine to form singlet excitons during the phosphorescence spectrum measurement. The spectrum taken in the phosphorescence time window at low temperature may consequently consist of both singlet and triplet emission.Publisher PDFPeer reviewe

Judicious heteroatom doping produces high performance deep blue/near UV multiresonant thermally activated delayed fluorescence OLEDs

Funding: Horizon 2020 Framework Programme - 838885; Leverhulme Trust - RPG-2016-047; Engineering and Physical Sciences Research Council - EP/L017008, EP/P010482/1; Fonds de la Recherche Scientifiques de Belgique - 2.5020.11; Walloon Region - n1117545; Fonds De La Recherche Scientifique - FNRS - F.4534.21.Two multiresonant thermally activated delayed fluorescence (MR-TADF) emitters are presented and it is shown how further borylation of a deep-blue MR-TADF emitter, DIDOBNA-N, both blueshifts and narrows the emission producing a new near-UV MR-TADF emitter, MesB-DIDOBNA-N, are shown. DIDOBNA-N emits bright blue light (ΦPL = 444 nm, FWHM = 64 nm, ΦPL = 81%, τd = 23 ms, 1.5 wt% in TSPO1). The deep-blue organic light-emitting diode (OLED) based on this twisted MR-TADF compound shows a very high maximum external quantum efficiency (EQEmax) of 15.3% for a device with CIEy of 0.073. The fused planar MR-TADF emitter, MesB-DIDOBNA-N shows efficient and narrowband near-UV emission (λPL = 402 nm, FWHM = 19 nm, ΦPL = 74.7%, τd = 133 ms, 1.5 wt% in TSPO1). The best OLED with MesB-DIDOBNA-N, doped in a co-host, shows the highest efficiency reported for a near-UV OLED at 16.2%. With a CIEy coordinate of 0.049, this device also shows the bluest EL reported for a MR-TADF OLED to date.Publisher PDFPeer reviewe