Chiral Thermally Activated Delayed Fluorescence-Active Macrocycles Displaying Efficient Circularly Polarized Electroluminescence

Open AccessCCS ChemistryRESEARCH ARTICLE7 Nov 2022Chiral Thermally Activated Delayed Fluorescence-Active Macrocycles Displaying Efficient Circularly Polarized Electroluminescence Wen-Long Zhao, Yin-Feng Wang, Shi-Peng Wan, Hai-Yan Lu, Meng Li and Chuan-Feng Chen Wen-Long Zhao School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 , Yin-Feng Wang School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 , Shi-Peng Wan School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049 , Hai-Yan Lu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049 , Meng Li *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 and Chuan-Feng Chen *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 https://doi.org/10.31635/ccschem.021.202101509 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail An efficient strategy for constructing chiral macrocycles with both thermally activated delayed fluorescence (TADF) and highly efficient circularly polarized electroluminescence (CPEL) properties was developed. Consequently, a pair of macrocyclic enantiomers (+)-(R,R)- MC and (−)-(S,S)- MC was synthesized by a combination of chiral octahydro-binaphthol moiety with triazine-based TADF skeleton. The chiral macrocycles exhibited obvious TADF properties with a low ΔEST of 0.067 eV, aggregation-induced emission behaviors, and high photoluminescence quantum yields of up to 79.7%. Moreover, the macrocyclic enantiomers showed mirror images in circular dichroism spectra and circularly polarized luminescence signals. Especially, the chiral macrocycles were suitable for the preparation of solution-processed circularly polarized organic light-emitting diodes, which displayed excellent device performances with a high maximum external quantum efficiency of up to 17.1%, low-efficiency roll-off of 3.5% at 1000 cd m−2, and intense CPEL along with electroluminescence dissymmetry factor of 1.7 × 10−3. Download figure Download PowerPoint Introduction Chiral macrocycles1 have drawn much attention in the last century for their wide applications in many research areas.2–7 Recently, the chiral macrocycles with circularly polarized photoluminescence (CPPL) properties have been of particular interest and ambition for researchers due to their potential applications in the design and construction of chiral supramolecular materials8–11 and chiral optoelectronic materials.12–15 However, such macrocycles with CPPL properties are still limited.16 Especially, no chiral macrocycles with circularly polarized electroluminescence (CPEL) properties17,18 have been reported so far, probably due to the difficulties in their achievement and the generally low external quantum efficiencies (EQEs) of such devices. Since thermally activated delayed fluorescence (TADF)19,20 emitters could up-convert triplet exciton through reverse intersystem crossing (RISC) to theoretically achieve an internal quantum efficiency (IQE) of 100%. They are considered the third generation of organic light-emitting diode (OLED) materials.21–23 In recent years, synthetic macrocycles with TADF properties have also attracted increasing interest for their unique structures and specific photophysical properties (Figure 1a). In 2018, Su and Huang's group24 reported a type of sulfone-based macrocycles with deep-blue TADF properties. Soon after, our group synthesized a series of oxacalixarenes based on the triazine moiety and also found that the macrocycles exhibited significant TADF activities.25 In 2020, Minakata et al.26 reported a π-conjugated TADF macrocycle and fabricated the corresponding OLED device with an EQE maximum (EQEmax) of 11.6%. This was also the first example of a macrocyclic emitter with TADF property utilized for OLED devices. More recently, Yasuda et al.27 reported a π-conjugated TADF macrocycle with efficient green TADF property, and the corresponding OLED device realized an EQEmax of 15.7%. However, examples with efficient combinations of macrocyclic structures and TADF properties are still limited, probably due to the difficulty in their design and synthesis. Chiral macrocycles with a simultaneous combination of chiral structures and TADF properties are very attractive, and they could also enrich the type of TADF materials, as well as expand the application of TADF to supramolecular chemistry; nevertheless, no such macrocycles have been hitherto reported. Especially, exploring the application of the chiral TADF macrocycles in highly efficient circularly polarized organic light-emitting diodes (CP-OLEDs) remains a challenge. Figure 1 | (a) The reported macrocycles with TADF properties. (b) The chiral macrocycles with TADF and CPEL properties in this work. Download figure Download PowerPoint Herein, we report a pair of chiral TADF macrocycles, namely (+)-(R,R)- MC and (−)-(S,S)- MC (Figure 1b), ingeniously combined by TADF skeleton with chiral octahydro-binaphthol subunit. The chiral macrocycles showed TADF properties with a small ΔEST of 0.067 eV, evident aggregation-induced emission (AIE) characteristics, and high photoluminescence quantum yields (PLQYs) of up to 79.7%. Moreover, the macrocyclic enantiomers also exhibited mirror-imaged circular dichroism (CD) signals and circularly polarized luminescence (CPL) properties with a dissymmetry factor (|gPL|) of 2.2 × 10−3 in solution. Especially, the solution-processed CP-OLEDs based on the macrocyclic enantiomers displayed high EQEmax of up to 17.1% and CPEL properties with |gEL| of 1.7 × 10−3. This work provides the first chiral macrocycles with TADF activities, and it also opens a new gate for the design and applications of the macrocyclic enantiomers in highly efficient CP-OLED devices. Experimental Methods All the reagents and solvents used were commercially available and used without further purification. 1H and 13C NMR spectra were recorded on AVIII 500 MHz NMR spectrometer (Bruker, Beijing, China) in CDCl3 solution. High-resolution mass spectra were measured on a Thermo Fisher® Exactive high-resolution liquid chromatography mass spectrometry (LC-MS) spectrometer (Beijing, China). The calculation was carried out with the Gaussian 09 software package ( https://gaussian.com/glossary/g09/). Geometry optimizations were conducted under the B3LYP/6-31G(d,p) level of density functional theory (DFT). Crystal structures were solved with direct methods and refined with a full-matrix least-squares technique, using the SHELXS software package ( ftp://10.8.1.178/). UV–Vis spectra were recorded on PerkinElmer® UV/Vis/NIR spectrometer (Lambda 950; Beijing, China), and the fluorescence spectra were recorded on HITACHI® F-7000 Fluorescence spectrometer (Beijing, China) at room temperature. The transient photoluminescence decay characteristics, temperature dependence experiments, and absolute PLQY were measured on an Edinburgh Instruments FLS1000 spectrometer (Beijing, China). The CD spectra were recorded on a JASCO J810 spectropolarimeter (Beijing, China). CPL and CPEL spectra were recorded at a 200 nm min−1 scan speed with a commercialized instrument of JASCO CPL-300 (Beijing, China) at room temperature. Results and Discussion Chiral macrocycles (−)-(S,S)- MC and (+)-(R,R)- MC were easily synthesized by efficient two-step reactions. As shown in Scheme 1, by utilizing commercial (R)-/(S)-octahydro-binaphthol and cyanuric chloride as the starting materials, the (−)-(S,S)- CTC or (+)-(R,R)- CTC precursor was synthesized efficiently by a nucleophilic substitution reaction. Then, the target chiral macrocycles were obtained by Suzuki coupling reaction of the precursor and (4-(9,9-dimethylacridin-10(9H)-yl)phenyl)borate ester. Structures of the target chiral macrocycles were confirmed with 1H NMR, 13C NMR spectroscopy ( Supporting Information Figures S25–S32), high-resolution mass spectrometry, and single-crystal X-ray diffraction analysis. Then the enantiomeric purity of the synthesized chiral macrocycles was determined by high-performance liquid chromatography analysis with 99% enantiomeric excesses ( Supporting Information Figures S1–S3 and Table S1). Detailed experimental data are described in the Supporting Information. Scheme 1 | Synthetic routes of chiral macrocycles (−)-(S,S)/(+)-(R,R)-MC. Download figure Download PowerPoint In order to intuitively investigate the structure of chiral macrocycles, we attempted to cultivate single crystals of the enantiomers several times but failed. Thus, we obtained a single crystal of rac- MC, suitable for X-ray diffraction analysis via slow evaporation of its solution in a mixture of tetrahydrofuran and acetonitrile. The detailed data are summarized in Supporting Information Table S2. As shown in Figures 2a–2d, approximate hexagonal cavities of rac- MC were observed in the crystal structures, and the triazine acceptors extended almost parallel in the same direction. Moreover, a large dihedral angle of nearly 90° was observed between the 9,9-dimethyl-9,10-dihydroacridine (DMAC) unit and the triazine acceptor, conducive to the separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Moreover, multiple C–H⋯π interactions and hydrogen bonds were observed in a packing unit cell containing both (+)-(R,R)- MC and (−)-(S,S)- MC. Besides, the octahydro-binaphthol unit could not only be used as the chiral source but also provided a large steric hindrance to reduce the exciton annihilation of the chiral macrocycle at aggregation state conducive to low-efficiency roll-off at high current density.28 Figure 2 | Crystal structure of rac-MC: (a) top view and (b) side view. Crystal stacking of rac-MC showing (c) C–H⋯π interactions and (d) hydrogen bond interactions. Download figure Download PowerPoint Next, the HOMO–LUMO electronic distribution and ΔEST of rac- MC were studied by DFT calculations based on the B3LYP functional and a 6-31G(d,p) basis (see the Supporting Information Table S3 for details). As shown in Supporting Information Figure S6, LUMOs were mainly located on the triazine acceptors due to their intense electron-withdrawing ability, while the HOMOs were mainly distributed on the DMAC moieties. The obvious spatial electronic separation of HOMO and LUMO was essential for obtaining a small ΔEST. Subsequently, the singlet (S1) and triplet (T1) state energy levels of rac- MC were calculated to be 2.46 and 2.45 eV, respectively, resulting in a small ΔEST of 0.01 eV, which promoted an efficient RISC from T1 to S1, as well as efficient TADF activity. Moreover, although the electronic distribution indicated the nonparticipation of the octahydro-binaphthol unit in the chiral macrocycle, it might have efficiently induced the TADF units to show CD and CPL activities. With the chiral macrocycles in hand, their electrochemical properties were investigated by cyclic voltammetry (see Supporting Information Figures S7–S8 and Table S4). Based on the onset of the oxidation curve, the electrochemical HOMO level was estimated as −5.38 eV for (−)-(S,S)- MC. Combined with the optical band gap (Eg) of (−)-(S,S)- MC, determined to be 2.72 eV from the onset of the absorption band in a thin film (Figure 3a), the LUMO energy level was calculated to be −2.66 eV. Following this, the thermal stabilities of the enantiomers were studied. (−)-(S,S)- MC exhibited excellent thermal stability with a very high decomposition temperature (Td) of 420 °C ( Supporting Information Figure S4) and a glass transition temperature (Tg) of 306 °C ( Supporting Information Figure S5). The excellent thermal and configurational stabilities and electrochemical properties of the enantiomers were necessary for improving the performance of CP-OLEDs. Figure 3 | (a) Absorption and fluorescence spectra of (−)-(S,S)-MC in film states at room temperature, and the fluorescence and phosphorescence spectra of (−)-(S,S)-MC in neat film at 77 K. (b) Transient PL decay curve of (−)-(S,S)-MC in doped film (25 wt % (−)-(S,S)-MC: CBP) at room temperature. Download figure Download PowerPoint The photophysical properties of the (−)-(S,S)- MC and (+)-(R,R)- MC were similar ( Supporting Information Figures S9, S10, and S16–S19), as shown in the data summarized in Supporting Information Tables S5 and S7. With (−)-(S,S)- MC as the example, the absorption spectrum of (−)-(S,S)- MC in neat film exhibited a strong absorption band centered at 264 nm (Figure 3a) and was assigned to the intramolecular π–π* transition. A broad and weak absorption band at about 370 nm was also apparent, attributed to the intramolecular charge transfer (ICT) from DMAC units to triazine units. Additionally, the emission band of (−)-(S,S)- MC in neat film at room temperature was centered at 505 nm. Further, with an increase of solvent polarity, the absorption spectrum of (−)-(S,S)- MC showed almost no change ( Supporting Information Figure S11), while a remarkable redshift of its fluorescence bands from 512 (in toluene) to 624 nm (in dimethylformamide) was recorded ( Supporting Information Figure S12 and Table S6), demonstrating an ICT in the excited state. Meaningfully, the AIE behaviors of (−)-(S,S)- MC were also observed in tetrahydrofuran (THF)/H2O mixtures with different water fractions (fw) ( Supporting Information Figure S13). The emission intensity of (−)-(S,S)- MC was enhanced dramatically with a continued increase in fw (fw = 0% to fw = 99%). Besides, the delayed fluorescence lifetimes of (−)-(S,S)- MC were gradually prolonged with an increase in fw values ( Supporting Information Figure S14), indicating an aggregation-induced delayed fluorescence property of this chiral macrocycle. Benefiting from the excellent AIE properties, (−)-(S,S)- MC displayed a PLQY of 65.6% in the air and a high PLQY of 79.7% under vacuum in a film state (Table 1). The enhancement of the fluorescence intensity in vacuum was a key feature of TADF activity ( Supporting Information Figure S15). Table 1 | Physical Properties of (−)-(S,S)-MC λabsa (nm) λFLb (nm) λFLc (nm) λPhosd (nm) ES1e (eV) ET1f (eV) ΔESTg (meV) ΦPLQYh (%) ΦPLQYi (%) τPFj (ns) τDFj (μs) 370 505 500 510 2.691 2.624 67 65.6 79.7 42 12.9 aAbsorption maximum of (−)-(S,S)- MC. bFluorescence emission peak of (−)-(S,S)- MC. cFluorescence emission peak, measured at 77 K. dPhosphorescence emission peak, measured at 77 K. eS1 energy level (≈1240/λ). fT1 energy level (≈1240/λ). gΔEST = ES1 − ET1. hAbsolute PL quantum yield in air. iAbsolute PL quantum yield under vacuum. jτPF and τDF were measured in doped film (25 wt % (−)-(S,S)- MC: CBP). To further verify the TADF properties of the chiral macrocycles, we recorded the absorption and fluorescence spectra of (−)-(S,S)-MC in film states at room temperature and fluorescence and phosphorescence spectra in neat film state at 77 K. As shown in Figure 3a, the emission peak of (−)-(S,S)- MC at room temperature was 505 nm. The energy levels of S1 and T1 states were calculated to be 2.691 and 2.624 eV, respectively, according to the onset of corresponding spectra (Figure 3a). Thus, small ΔEST values of (−)-(S,S)- MC were estimated to be 0.067 eV in neat film at 77 K. In order to fabricate CP-OLEDs with high efficiencies, 4,4′-dicarbazolyl-1,1′-biphenyl (CBP) was selected as the host material. CBP had a high triplet energy level of 2.6 eV, which was sufficient to block the triplet excitons within the guest molecules.29,30 Similar to that of (−)-(S,S)- MC in neat film, the ΔEST value of (−)-(S,S)- MC in the doped film was estimated to be 0.068 eV. Also, the transient PL decay curves of (−)-(S,S)- MC were measured (Figure 3b). Two distinct lifetimes were visible the transient PL decay curve of (−)-(S,S)- MC in doped film at room temperature with prompt lifetime (τp) of 42 ns and delayed fluorescence lifetime (τd) of 12.9 μs. The short τd effectively suppressed the triplet-triplet annihilation (TTA) and singlet-triplet annihilation (STA) processes in the devices to realize low-efficiency roll-off.31 Next, the chiroptical properties of the macrocyclic enantiomers in toluene solutions and film states were investigated by CD and CPL spectra. The chiroptical data are summarized in Supporting Information Table S8. As shown in Figure 4a, (+)-(R,R)- MC and (−)-(S,S)- MC displayed mirror-imaged CD signals. The strong Cotton effects in a short wavelength region centered at about 300 nm were assigned to the π–π* transition absorption. Then the long-wavelength Cotton effects centered at about 374 nm were assigned to the ICT effect from DMAC unit to triazine unit, indicating that the octahydro-binaphthol induced the TADF skeleton successfully to produce chirality in the ground state. Subsequently, almost mirror-image CPL spectra of the enantiomers in toluene were also observed with the gPL of +2.2 × 10−3 for (+)-(R,R)- MC and −2.2 × 10−3 for (−)-(S,S)- MC (Figures 4a and 4b), which confirmed the chiroptical properties of the enantiomers in the excited state. Moreover, the CPL properties of the chiral macrocycles in film states were studied, and the chiral macrocycles in neat and doped films displayed intense CPL activities (Figure 4c). The |gPL| values of macrocyclic enantiomers were 2.0 × 10−3 for neat film and 1.7 × 10−3 for doped films, respectively (Figure 4d). Figure 4 | (a) CD and CPL spectra and (b) gPL versus wavelength curves of (+)-(R,R)/( −)-(S,S)-MC in toluene (c = 1 × 10−4 M). (c) CPL spectra and (d) gPL versus wavelength curves of (+)-(R,R)/(−)-(S,S)-MC in neat film, and doped film (25 wt % macrocyclic enantiomers: CBP). Download figure Download PowerPoint Encouraged by their good solubility, high PLQY, and intense CPL, (+)-(R,R)/( −)-(S,S)- MC were used as chiral emitters to fabricate the solution-processed CP-OLEDs.32,33 Subsequently, the device configuration was optimized by employing CBP as the host material. The configurations of devices A( R ) and A( S ) were as follows: ITO/PEDOT:PSS (50 nm)/CBP:25 wt % (+)-(R,R)/(−)-(S,S)- MC (40 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm), and details of the device configurations and chemical structures of adopted assistant materials are shown in Figure 5a. The devices' performances are illustrated in Figures 5b and 5c and Supporting Information Figures S21–S24, and the detailed data are summarized in Table 2. Devices A( R ) and A( S ) displayed the same EL spectra with the maximum peak at 522 nm and Commission Internationale de l'Eclairage (CIE) coordinates of (0.28, 0.54). The devices obtained displayed high efficiencies with a low turn-on voltage (VT) of 3.5 V, a maximum current efficiency (CEmax) of 53.7 cd A−1, a maximum power efficiency (PEmax) of 37.0 lm W−1, and an EQEmax of 17.1%. In addition, device A( R ) exhibited significantly low-efficiency roll-off with EQE values of 16.5% and 15.5% at the luminance of 1000 and 2000 cd m−2, respectively. Furthermore, the mirror-image CPEL signals with opposing gEL values of +1.5 × 10−3 and −1.7 × 10−3 for devices A( R ) and A( S ), respectively, were achieved. This result could be attributed to the high racemic energy barrier of octahydro-binaphthol, endowing the macrocyclic TADF enantiomers with a stable chiral conformation. Figure 5 | (a) Energy level diagrams and molecular structures of used materials of A(R) and A(S). (b) EQE-Luminance characteristics of A(R) and A(S). Inset: EL spectra of the devices at 6.8 V. (c) The CPEL and gEL values of the devices as a function of emission wavelength. Download figure Download PowerPoint Table 2 | The Chiral Macrocycles A( R) and A( S) Device Performances Device VTa (V) λELb (nm) Lmaxc (cd/m2) EQEd (%) Max/1000/2000 CEmaxe (cd A−1) PEmaxf (lm W−1) Efficiency Roll-Offg (%) A( R ) 3.8 522 14920 17.1/16.5/15.5 53.7 37.0 3.5/9.4 A( S ) 3.5 522 12900 15.5/15.3/14.5 48.8 34.9 1.3/6.4 aTurn-on voltage. bElectroluminescence peak of devices. cMaximum luminance. dEQE of maxima and at luminance of 1000, 2000 cd m−2, respectively. eMaximum current efficiency. fMaximum power efficiency. gEfficiency roll-off at luminance of 1000 and 2000 cd m−2, respectively. Conclusion We have developed an efficient strategy for constructing chiral macrocycles with both TADF and highly efficient CPEL properties. Consequently, a pair of chiral macrocycles (+)-(R,R)- MC and (−)-(S,S)- MC was conveniently obtained by a combination of chiral octahydro-binaphthol moiety with triazine-based TADF skeleton. The chiral macrocycles showed remarkable TADF properties with a low ΔEST of 0.067 eV, a short, delayed fluorescence lifetime of 1.5 μs, prominent AIE properties, and high PLQYs of up to 79.7%. Moreover, the chiral TADF-active macrocycles exhibited mirror-imaged CD and CPL properties with |gPL| of about 2.2 × 10−3. Notably, the solution-processed CP-OLEDs based on the macrocyclic enantiomers achieved EQEmax of up to 17.1%, a low-efficiency roll-off of 3.5% at 1000 cd m−2, and displayed intense CPEL signals with gEL of +1.5 × 10−3 and −1.7 × 10−3, respectively. We believe that this work not only provides a new perspective to develop high-performance CPEL materials but also opens a new avenue for the practical application of chiral macrocycles. Supporting Information Supporting Information is available and includes supplemental experimental details, Figures S1–S32, and Tables S1–S8. Conflict of Interest The authors declare no conflict of interest. Funding Information This work was supported by the National Natural Science Foundation of China (nos. 21971235, 91956119, 22122111, and 92056109), Beijing National Laboratory for Molecular Sciences (no. BNLMS-CXXM-202105), and Youth Innovation Promotion Association CAS (no. 2019034). Preprint Statement Research presented in this article was posted on a preprint server prior to publication in CCS Chemistry. The corresponding preprint article can be found here: DOI: 10.31635/ccschem.021.202101509. References 1. Neri P.; Sessler J. L.; Wang M.-X.Calixarenes and Beyond; Springer: Switzerland, 2016. Google Scholar 2. 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