Open Access Article
Cheng-Zhuo
Du†
a,
Minqiang
Mai†
b,
Pei-Han
Gao
a,
Yi-Chao
Zhao
a,
Xiang-Yu
Gao
a,
Dongdong
Zhang
*b,
Lian
Duan
*b,
Chunming
Cui
a and
Xiao-Ye
Wang
*ac
aState Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Haihe Laboratory of Sustainable Chemical Transformations, Academy for Advanced Interdisciplinary Studies, College of Chemistry, Nankai University, Tianjin, 300071, China. E-mail: xiaoye.wang@nankai.edu.cn; Web: http://wang.nankai.edu.cn
bKey Lab of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084, China. E-mail: ddzhang@mail.tsinghua.edu.cn; duanl@mail.tsinghua.edu.cn
cBeijing National Laboratory for Molecular Sciences, Beijing, 100190, China
First published on 12th January 2026
Multi-resonance (MR) materials based on 1,4-BN-heteroarenes have attracted extensive attention in recent years for their narrowband electroluminescence. Extending the π-conjugation of MR skeletons is a widely adopted strategy to regulate their emission colors, but it inevitably induces structural distortion and undesirable vibronic couplings, thus broadening the emission bandwidth. Herein, we design and synthesize new MR emitters via π-extension of a classic MR backbone (CzBN) and disclose how the twisted structure plays a positive role in reducing the emission bandwidth. Specifically, π-extension of CzBN to form a [5]helicene substructure (BN-5H) induces serious vibrations, while further extending the helicene moiety to build a [7]helicene substructure (BN-7H) suppresses undesirable vibrations by locking the conformation. As a consequence, BN-7H achieves a smaller full-width at half-maximum (FWHM) of 28 nm compared with BN-5H (33 nm) in organic light-emitting diodes and longer device lifetime. These results overturn the traditional cognition of the detrimental effect of highly twisted structures on narrowband emission and offer a new design concept for the future development of narrowband electroluminescence materials.
Herein, we design and synthesize new MR emitters (BN-5H and BN-7H) via π-extension of CzBN and disclose the positive effect of the twisted structure on narrowband electroluminescence (Fig. 1). BN-5H, comprising a [5]helicene substructure, exhibits serious structural vibrations similar to those of previously reported CzBN derivatives.13,17 In contrast, BN-7H, with an elongated [7]helicene moiety, significantly suppresses the undesirable vibrations by locking the conformation. Moreover, the highly twisted structure of BN-7H also suppresses solid-state emission quenching and spectral broadening, which are common problems for planar MR emitters.22–24 Therefore, BN-7H achieves a smaller FWHM of only 28 nm (0.12 eV) compared with BN-5H (33 nm/0.16 eV) in OLEDs. The FWHM of BN-7H is the smallest among the reported green MR materials based on benzene-fused CzBN derivatives. Besides, a high maximum external quantum efficiency (EQEmax) of 26.2% and long operation lifetime of 560.1 h at 1000 cd m−2 are obtained for BN-7H-based devices. These results shed new light on the positive role of twisted helicene structures for narrowband electroluminescence materials.
![]() | ||
| Scheme 1 Synthetic routes to BN-5H and BN-7H. DMF: N,N-dimethylformamide; DIPEA: N,N-diisopropylethylamine; and o-DCB: 1,2-dichlorobenzene. | ||
To further understand the geometric and electronic properties of BN-5H and BN-7H, time-dependent density functional theory (TD-DFT) calculations were performed at the B3LYP/6-311G(d,p) level. Compared with BN-5H, BN-7H features a more twisted geometry, with a dihedral angle of 44.98° between the terminal benzene rings (Fig. S13). According to the optimized geometries, the root-mean-square deviation (RMSD) values between S0 and S1 states were calculated to be 0.107 Å and 0.091 Å for BN-5H and BN-7H, respectively (Fig. 2A). Moreover, the total reorganization energy (λ) of BN-7H (0.125 eV) is much smaller than that of BN-5H (0.380 eV). These results indicate that the structural relaxation is effectively suppressed by further extending the helicene moiety.
To gain a deeper understanding of the vibronic coupling of BN-5H and BN-7H, the Huang-Rhys (HR) factors and λ at different vibrational modes were calculated using the Molecular Materials Property Prediction Package (MOMAP) software (Fig. 2B).28 For BN-5H, two large HR factors of 0.95 and 0.48 are observed in the low-frequency region, which are related to the out-of-plane twisting vibrations of the MR framework and the peripheral tert-butyl groups (Modes 1 and 33). Moreover, the high-frequency stretching vibrational modes 153 (1254.78 cm−1) and 204 (1589.96 cm−1) of BN-5H contribute significantly to λ (Fig. S14), which may induce obvious spectral broadening. In contrast, BN-7H displays significantly suppressed out-of-plane skeleton twisting vibrations (Modes 2, 7, 9) with smaller HR factors (0.54, 0.47, 0.40) in the region 14.52–50.94 cm−1. The suppressed vibrations of BN-7H can be attributed to the strong intramolecular noncovalent interactions from the terminal benzene rings, which can be visualized by the reduced density gradient (RDG) analysis (Fig. 2D).29 Besides, compared with BN-5H, the high-frequency stretching vibrations of BN-7H are almost negligible (Fig. S15). These results reveal the feasibility of introducing highly twisted structure to restrain common vibrations of MR emitters.
The photophysical properties of BN-5H and BN-7H were further studied in toluene solutions (1 × 10−5 M) (Fig. 3A and B), and the detailed data are summarized in Table 1. BN-5H and BN-7H exhibit strong absorption bands peaking at 488 nm and 508 nm, with molar extinction coefficients (ε) of 47
830 M−1 cm−1 and 56
320 M−1 cm−1, respectively. The fluorescence maximum of BN-7H (524 nm) shows an obvious red-shift of 18 nm compared with that of BN-5H (506 nm) due to the π-extension. Benefiting from the suppressed vibrations by locking the conformation, BN-7H achieves a smaller FWHM value of only 23 nm (0.10 eV) in toluene than BN-5H (27 nm/0.13 eV). The Commission Internationale de L'Eclairage (CIE) coordinate of BN-7H is (0.22, 0.72), meeting the green color requirement of (0.21, 0.71) stipulated by the National Television System Committee (NTSC). Moreover, BN-7H exhibits a higher photoluminescence quantum yield (PLQY) of 95% than BN-5H (86%) due to the suppression of undesirable vibrations.
| Compound | λ abs (nm) | λ PL (nm) | FWHMb (nm/eV) | ΔESTc (eV) | HOMO/LUMOd (eV) | E g CV (eV) | PLQYe (%) | τ (ns) | k r (108 s−1) | k nr (107 s−1) | T d/Tgh (°C) | CIE (x, y)i |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| a Maximum wavelength of UV-vis absorption and fluorescence spectra in toluene solution (1 × 10−5 M) at 298 K. b FWHMs of the fluorescence spectra. c Obtained from the peak of the fluorescence and phosphorescence spectra in toluene solution at 77 K. d Obtained from the onset potentials of the first oxidative and reductive waves of CV curves, respectively. e Absolute photoluminescence quantum yield measured in oxygen-free toluene solution. f Fluorescence lifetime. g Radiative decay rate constant and non-radiative decay rate constant. h Decomposition temperature (Td) and glass transition temperature (Tg). i Commission Internationale de L'Eclairage (CIE) coordinates in the CIE 1931 chromaticity diagram. | ||||||||||||
| BN-5H | 488 | 506 | 27/0.13 | 0.50 | −5.42/–2.97 | 2.45 | 86 | 5.3 | 1.6 | 2.6 | 503/- | (0.14, 0.68) |
| BN-7H | 508 | 524 | 23/0.10 | 0.29 | −5.40/–3.01 | 2.39 | 95 | 4.0 | 2.4 | 1.3 | 547/258 | (0.22, 0.72) |
The transient photoluminescence spectra were next examined, and no obvious delayed components were observed in degassed solutions (Fig. S5), implying that these two emitters are fluorescence materials without thermally activated delayed fluorescence (TADF) characteristics, which may be associated with the large singlet-triplet energy gaps (ΔEST) of 0.50 eV for BN-5H and 0.29 eV for BN-7H (Fig. S3).30–33 The reduction of ΔEST of BN-7H is further investigated by the hole–electron analysis (Fig. S12). The fluorescence lifetimes (τ) were determined to be 5.3 ns and 4.0 ns for BN-5H and BN-7H, respectively, and the corresponding radiative decay rates (kr) and nonradiative decay rates (knr) of BN-5H and BN-7H were calculated and are summarized in Table 1. BN-7H displays a faster radiative decay process with kr of 2.4 × 108 s−1 and a significantly suppressed knr of only 1.3 × 107 s−1, while BN-5H suffers from a more serious energy loss with knr of 2.6 × 107 s−1. This difference indicates that the more twisted structure of BN-7H can lock the flexible conformation and suppress undesirable vibrations to reduce nonradiative energy dissipation.
The emission properties of the two compounds in solid state were then investigated (Fig. 3C), and 1,3-dihydro-1,1-dimethyl-3-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)indeno[2,1-b]carbazole (DMIC-TRZ) was chosen as the wide-energy-gap host.34 As the dopant concentration increases, the emission spectra of BN-5H doped films are significantly broadened with FWHM values increasing from 33 nm to 37 nm, while the FWHMs of BN-7H-doped films are basically unchanged (FWHM: 31 nm) (Fig. 3D). Moreover, the concentration-dependent emission quenching of BN-7H is also efficiently suppressed compared with BN-5H (Table S2). These results demonstrate the beneficial effect of highly twisted structures beyond vibrational suppression at the molecular level.
Considering that BN-5H and BN-7H are fluorescence emitters, TADF-sensitized OLEDs were fabricated to evaluate the electroluminescent (EL) properties. The corresponding energy level scheme and chemical structures of the materials used are depicted in Fig. 4A and S17. Particularly, 2,4,6-tris(2-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(trifluoromethyl)phenyl)-1,3,5-triazine (3CTF) was chosen as the TADF sensitizer because of its small molecular dipole moment, substantial spectral overlap with these emitters, and high reverse intersystem crossing rate of 2.57 × 106 s−1 (Fig. S18).35 The EL characteristics are summarized in Table 2. Obviously, the devices based on BN-5H show lower tolerance to the dopant concentration, and the FWHM increases significantly with higher dopant concentrations (Fig. 4B). By contrast, the BN-7H-based devices display nearly unchanged emission peaks and FWHMs with increased dopant concentrations, and pure green emissions peaking at 527–529 nm with small FWHMs of only 28–30 nm (0.12–0.13 eV) were recorded (Fig. 4C). Such a result is one of the smallest FWHMs among the reported sensitized green OLEDs (Table S5).3,36–43 Besides, the CIE coordinates of BN-7H devices reach (0.24, 0.69), which is very close to the pure green requirement of the NTSC standard. Moreover, BN-7H shows outstanding device performance with EQEmax, current efficiency (CE), and power efficiency (PE) of 26.2%, 102.3 cd A−1, and 106.5 lm W−1, respectively (Fig. 4E). Meanwhile, the efficiency roll-off is especially low with the EQE remaining 21.2% at 1000 cd m−2.
| Emitter | Dopant concentration (wt%) | λ EL (nm) | FWHMb (nm/eV) | V on (V) | L max (cd m−2) | CEmaxe (cd A−1) | PEmaxf (lm W−1) | EQEg (%) | CIE (x, y)h |
|---|---|---|---|---|---|---|---|---|---|
| a The maximum EL wavelength. b FWHM of the EL spectrum. c Turn-on voltage at 1 cd m−2. d Maximum luminance. e Maximum CE. f Maximum PE. g Maximum EQE, and values at 100 cd m−2 and 1000 cd m−2. h CIE coordinates of the devices in the CIE 1931 chromaticity diagram. | |||||||||
| BN-5H | 1 | 507 | 34/0.16 | 2.6 | 42 450 |
77.1 | 78.2 | 25.6/25.6/24.6 | (0.19.0.62) |
| 2 | 509 | 33/0.16 | 2.6 | 40 090 |
76.6 | 74.8 | 24.1/24.0/22.9 | (0.19.0.65) | |
| 3 | 511 | 35/0.17 | 2.7 | 39 750 |
71.8 | 73.9 | 21.8/21.6/19.8 | (0.20.0.66) | |
| 4 | 513 | 39/0.18 | 2.7 | 34 360 |
67.7 | 67.0 | 19.7/19.3/17.6 | (0.23.0.67) | |
| BN-7H | 1 | 527 | 28/0.12 | 2.6 | 47 370 |
102.3 | 106.5 | 26.2/26.2/21.2 | (0.24.0.69) |
| 2 | 527 | 28/0.12 | 2.6 | 51 720 |
99.8 | 110.8 | 25.0/24.6/22.0 | (0.25.0.69) | |
| 3 | 527 | 29/0.13 | 2.6 | 46 890 |
81.0 | 90.9 | 20.3/19.7/16.6 | (0.26.0.69) | |
| 4 | 529 | 30/0.13 | 2.6 | 38 610 |
82.0 | 92.0 | 20.7/18.8/15.4 | (0.27.0.69) | |
We further evaluated the operational stabilities of these devices under an initial luminance (L0) of 5000 cd m−2 (Fig. 4F). The LT90 (lifetime to 90% of the initial luminance) of 14.5 and 33.5 h were recorded for BN-5H and BN-7H, respectively. By adopting a degradation acceleration factor (n) of 1.75,44 the LT90 at 1000 cd m−2 can be extrapolated as 242.4 h for BN-5H and 560.1 h for BN-7H, respectively. The device lifetime of BN-7H is more than twice that of BN-5H, indicating the advantages of the highly twisted structure in improving device stability.
Furthermore, it is noteworthy that BN-7H is chiral, with higher configurational stability than BN-5H due to the spatial overlapping between the terminal benzene rings (Fig. S26). Therefore, the P and M enantiomers of BN-7H were successfully separated by chiral high-performance liquid chromatography (HPLC) (Fig. S22). BN-7H exhibits circular dichroism (CD) responses with the largest absolute absorption dissymmetry factors (|gabs|) of 0.009 at 379 nm (Fig. S24), as well as circularly polarized luminescence (CPL) with the luminescence dissymmetry factors (|glum|) of 0.7 × 10−3 at 524 nm and CPL brightness (BCPL) of 19.0 M−1 cm−1 (Fig. S25), which are comparable to most of the reported circularly polarized MR materials (Table S6).45–49 However, due to the limited solubility hindering the large-scale chiral separation, the EL properties of BN-7H enantiomers were not studied. Further optimizing the molecular structures and chiral separation conditions can provide promising materials for circularly polarized OLEDs with narrowband emissions in the future.14,50–54
Footnote |
| † These authors contributed equally. |
| This journal is © The Royal Society of Chemistry 2026 |