Highly Efficient Thermally Activated Delayed Fluorescence from an Excited-State Intramolecular Proton Transfer System

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1 Supporting Information Highly Efficient Thermally Activated Delayed Fluorescence from an Excited-State Intramolecular Proton Transfer System Masashi Mamada*, Ko Inada, Takeshi Komino, William J. Potscavage, Jr., Hajime Nakanotani, Chihaya Adachi* Center for Organic Photonics and Electronics Research (OPERA), Kyushu University 744 Motooka, Nishi, Fukuoka , Japan Contents: Methods S1. Synthesis... 3 Figure S1. Thermogravimetric (TG) and differential thermal analysis (DTA)... 5 Figure S2. Photodegradation evaluation... 5 Methods S2. X-ray crystallographic structure determinations... 6 Figure S3. Crystal structure of TQB... 6 Table S1. Crystal data and structure refinement for TQB... 7 Methods S3. Ground state and excited state calculations... 8 Table S2. Calculated ground-state and vertical excitation energies... 8 Table S3. Calculated adiabatic excitation energies... 9 Figure S4. 3D coutour maps of calculated 2D PES plots... 9 Figure S5. Natural transition orbitals and overlap integrals of hole and electron distributions Figure S6. UV-Vis absorption and PL spectra Table S4. Photophysical properties of TQB Figure S7. PL transient decay spectra of TQB Figure S8. UV-Vis absorption and PL spectra of a-qd Table S5. Photophysical properties of a-qd Figure S9. PL transient decay spectra of a-qd Table S6. Photophysical properties of temperature dependence for a TQB-doped film of DPEPO Figure S10. Transient PL characteristics of a TQB-doped film of DPEPO Figure S11. Temperature dependence of PL quantum efficiencies Figure S12. PL decay of TQB neat film

2 Figure S13. DF intensity dependence on laser fluence Figure S14. Arrhenius plot of the reverse ISC rate from the triplet to the singlet state Figure S15. Cyclic voltammograms for TQB Figure S16. Photoelectron yield spectroscopy measurements of TQB Figure S17. Energy levels diagram of host materials and TQB Figure S18. PL and EL spectra for TQB-doped films Table S7. TQB-based OLED characteristics Figure S19. The computationally calculated radical states Table S8. Calculated cation and anion radical energies for TQB Methods S4. Angular dependent PL measurements Figure S20. Radiation patterns from angular dependent PL measurements Table S9. Materials Table S10. Instrumentas Data S1. NMR spectra Data S2. FT-IR spectra Table S11. Optimized geometry for the S 0 of TQB-TA Table S12. Optimized geometry for the S 0 of TQB-TC Table S13. Optimized geometry for the S 0 of TQB-TD Table S14. Optimized geometry for the S 1 state of TQB-TA Table S15. Optimized geometry for the S 1 state of TQB-TB Table S16. Optimized geometry for the S 1 state of TQB-TC Table S17. Optimized geometry for the S 1 state of TQB-TD Table S18. Optimized geometry for the T 1 state of TQB-TA Table S19. Optimized geometry for the T 1 state of TQB-TB Table S20. Optimized geometry for the T 1 state of TQB-TC Table S21. Optimized geometry for the T 1 state of TQB-TD Table S22. Optimized geometry for the M + of TQB-TA Table S23. Optimized geometry for the M + of TQB-TB Table S24. Optimized geometry for the M + of TQB-TC Table S25. Optimized geometry for the M + of TQB-TD Table S26. Optimized geometry for the M of TQB-TA Table S27. Optimized geometry for the M of TQB-TB Table S28. Optimized geometry for the M of TQB-TC Table S29. Optimized geometry for the M of TQB-TD Table S30. Optimized geometry for the S 0 of a-qd-ta Table S31. Optimized geometry for the S 1 of a-qd-tb Table S32. Optimized geometry for the T 1 state of a-qd-tb Supplementary references

3 Methods S1. Synthesis Triquinolonobenzene (TQB) was prepared according to the literature, 1 and 5,13-dihydrodibenzo[b,j][1,7]- phenanthroline-8,14-dione (angular quinacridone) was synthesized using a similar method. Procedure for the synthesis of 1 and 2 A mixture of 1,3,5-tribromobenzene (4.71 g, 15.0 mmol), anthranilic acid (9.24 g, 67.5 mmol), anhydrous potassium carbonate (9.32 g, 67.5 mmol), copper powder (0.12 g, 1.89 mmol), copper(i) chloride (0.15 g, 1.52 mmol), and copper (II) acetate monohydrate (0.03 g, 0.15 mmol) in 1-pentanol (50 ml) was refluxed overnight in a round-bottom flask fitted with a Dean-Stark apparatus to remove water. After cooling, 1-pentanol was removed in vacuo and water was added. The resulting solution was filtered and the filtrate was acidified with concentrated hydrochloric acid. The precipitated solid was filtered, washed with water, 50% acetic acid, and water, and dried. The crude product was purified by recrystallization from DMF/water to give compound 1. For compound 2, 1,3-dibromobenzene was used instead of 1,3,5-tribromobenzene. Another synthetic method for compound 1 has been reported in the literature. 2 Procedure for the synthesis of TQB and angular-shape quinacridone a-qd Compound 1 (4.00 g, 8.28 mmol) or compound 2 (3.00 g, 8.62 mmol) and polyphosphoric acid (60 g) were heated for 150 C for 6 h. After cooling, water was added and the reaction mixture was filtered, washed with water and dried. The resulting solid was washed with boiling acetic acid and DMF. The crude product was purified by vacuum sublimation ( C at a pressure of 10 2 Pa) to give pure product TQB or a-qd. Compound 1: 93%. Mp: >300 C. 1 H-NMR: δ/ppm (500 MHz, DMSO-d 6, 300 K) = (br, 3H); 9.56 (s, 3H); 7.88 (d, 3H, J = 7.8 Hz); 7.44 (dd, 3H, J = 7.9 Hz, J = 8.9 Hz); 7.37 (d, 3H, J = 7.9 Hz); 6.80 (dd, 3H, J = 7.9 Hz, J = 8.9 Hz); 6.75 (s, 3H). 13 C-NMR: δ/ppm (125 MHz, DMSO-d 6 ) = , , , , , , , , MS/ASAP: m/z 483 (M +, 100%). 3

4 Compound 2: 77%. Mp: >300 C. 1 H-NMR: δ/ppm (500 MHz, DMSO-d 6, 300 K) = (br, 2H); 9.60 (br, 2H); 7.89 (d, 2H); 7.41 (dd, 2H, J = 7.9 Hz); 7.30 (d, 2H, J = 7.8 Hz); 7.29 (t, 1H, J = 7.8 Hz); 7.08 (s, 1H); 6.92 (d, 2H, J = 7.9 Hz); 6.78 (dd, 2H, J = 7.9 Hz). 13 C-NMR: δ/ppm (125 MHz, DMSO-d 6 ) = , , , , , , , , , , MS/ASAP: m/z 348 (M +, 100%). HOOC HN O HN PPA O HOOC N H NH COOH N H O NH 1 TQB TQB: colorless crystals. 39%. Mp: >400 C. 5% weight loss temperature: 466 C. 1 H-NMR: δ/ppm (500 MHz, DMSO-d 6, 393 K) = (br, 3H); 8.47 (d, J = 7.8 Hz, 3H); 7.90 (m, 6H); 7.56 (m, 3H). 13 C-NMR could not be taken due to the low solubility. MS/ASAP: m/z 429 (M +, 100%). IR: ν max /cm 1 = 3482, 2838, 1634, 1602, 1558, 1508, 1473, 1443, 1362, 1342, 1219, 1175, 1151, 1111, 1013, 839, 755, 742, 669, 639, 610, 540. Anal. Calcd. For C 27 H 15 N 3 O 3 : C, 75.52; H, 3.52; N, 9.79; O, Found: C, 75.58; H, 3.47; N, a-qd: pale yellow crystals. 43%. Mp: >400 C. 5% weight loss temperature: 432 C. 1 H-NMR: δ/ppm (500 MHz, DMSO-d 6, 300 K) = (br, 1H); (br, 1H); 8.47 (d, 1H, J = 9.0 Hz); 8.37 (d, 1H, J = 8.2 Hz); 8.28 (d, 1H, J = 8.2 Hz); 7.85 (dd, 1H, J = 8.1 Hz); 7.82 (d, 1H, J = 8.4 Hz); 7.78 (dd, 1H, J = 8.2 Hz); 7.70 (d, 1H, J = 8.2 Hz); 7.46 (dd, 1H, J = 8.2 Hz); 7.38 (dd, 1H, J = 7.8 Hz); 7.33 (d, 1H, J = 9.0 Hz). 13 C-NMR could not be taken due to the low solubility. MS/ASAP: m/z 312 (M +, 100%). IR: ν max /cm 1 = 3448, 2976, 1630, 1607, 1542, 1518, 1473, 1448, 1370, 1323, 1292, 1257, 1232, 1189, 1171, 1156, 1116, 1010, 822, 753, 740, 669, 640, 618, 595, 566, 541. Anal. Calcd. For C 20 H 12 N 2 O 2 : C, 76.91; H, 3.87; N, 8.97; O, Found: C, 77.02; H, 3.87; N,

5 Figure S1. Thermogravimetric (TG) and differential thermal analysis (DTA). (a) TG-DTA at ambient pressure for TQB. (b) TG-DTA at ambient pressure for a-qd. (c) TG at 1 Pa for TQB, (d) TG at 1 Pa for a-qd. Figure S2. Photodegradation evaluation. (a) The PL intensity normalized to the initial of TQB and 4CzIPN neat films as a function of time under continuous excitation UV irradiation ( nm) in ambient condition. (b) Transmittance spectra for 100 nm films of TQB and 4CzIPN for the estimation of the density of excitons 5

6 Methods S2. X-ray crystallographic structure determinations X-ray diffraction data for TQB were collected on a Rigaku Saturn 724 CCD diffractometer with Mo-Kα radiation (λ = Å) at 123 K. Single crystals of TQB suitable for X-ray analysis were grown by slow sublimation under under continuous N 2 flow. Data collection, cell refinement, and data reduction were carried out using the software CrystalClear-SM. 3 The structure was solved by direct methods using the program SHELXS-97, 4 and refined by fullmatrix least squares methods on F 2 using SHELXL All materials for publication were prepared using the software Yadokari-XG ,7 All non-hydrogen atoms were refined anisotropically. The positions of all hydrogen atoms were calculated geometrically and refined as a riding model. Crystallographic data have been deposited with Cambridge Crystallographic Data Centre (CCDC): Deposition number CCDC Copies of the data can be obtained free of charge via Figure S3. Crystal structure of TQB. (a) ORTEP drawing of the asymmetric unit with thermal ellipsoids at 50% probability. (b) Front view with disorder. (c) Side view. (d) Packing arrangement of TQB along with the c-axis 6

7 Table S1. Crystal data and structure refinement for TQB Identification code TQB Empirical formula C 27 H 15 N 3 O 3 Formula weight Temperature 123 K Wavelength Å Crystal system orthorhombic Space group P c c n Unit cell dimensions a = (17) Å α = 90. b = (9) Å β = 90. c = (12) Å γ = 90. Volume (15) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient mm -1 F(000) 888 Crystal size 0.12 x 0.04 x 0.03 mm 3 Theta range for data collection to Index ranges -4<=h<=4, -24<=k<=18, -33<=l<=32 Reflections collected Independent reflections 2119 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2119 / 576 / 262 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.å -3 7

8 Table S2. Calculated ground-state and vertical excitation energies. Calculated ground-state S 0 energy and first vertical excitation energy (VEE), absorption wavelength, and oscillator strength (f) of S 1 and T 1 for TQB and a-qd at the B3LYP/6-31++G(d,p) level Structure Methods S3. Ground state and excited state calculations The computations were mainly performed using the computer facilities at the Research Institute for Information Technology, Kyushu University. Molecular orbital calculations were performed using the programs Gaussian 09 and Gaussian 16. 8,9 Gaussian 16 was used for the calculation of the potential energy surface map because of the new feature of TD-DFT analytic second derivatives for predicting vibrational frequencies, which greatly reduced the calculation time. The results for the energies at the stationary points should be the same for both programs. The geometries were optimized at the B3LYP/6-31++G(d,p) level using Gaussian 09. The presence of energy minima was confirmed by the absence of imaginary modes (no imaginary frequencies). The time-dependent density functional theory (TD-DFT) calculations were conducted at the B3LYP/6-31++G(d,p) level. To numerically achieve accurate values, we have used a fine grid. The potential energy surface (PES) maps were calculated at the B3LYP/6-31++G(d,p) level using Gaussian 16. The solvation effect in a solvent of toluene was considered by using the polarizable continuum model (PCM) for PES calculations. The overlap integrals of the hole and electron distributions were calculated using the program Multiwfn. 10 The radical cation and anion energies were calculated at the B3LYP/6-31++G(d,p) level. Groundstate S 0 [ev] S 1 -vertical [ev] TQB-TA TQB-TB TQB-TC TQB-TD a-qd-ta a-qd-tb Singlet VEE T 1 -vertical [ev] Excited state 1: 3.37 ev, 368 nm, f = Excited state 2: ev, 353 nm, f = Excited state 3: 3.65 ev, 339 nm, f = TQB-TA geometry a Excited state 1: 2.96 ev, 419 nm, f = Excited state 2: ev, 396 nm, f = Excited state 3: 3.27 ev, 379 nm, f = Excited state 1: 3.38 ev, 366 nm, f = Excited state 2: ev, 352 nm, f = Excited state 3: 3.54 ev, 350 nm, f = Excited state 1: 3.08 ev, 403 nm, f = Excited state 2: ev, 350 nm, f = Excited state 3: 3.65 ev, 340 nm, f = a-qd-ta geometry a Triplet VEE Excited state 1: 2.82 ev, 439 nm, f = 0 Excited state 2: 2.98 ev, 416 nm, f = 0 Excited state 3: 2.98 ev, 416 nm, f = 0 Excited state 1: 2.49 ev, 498 nm, f = 0 Excited state 2: 2.62 ev, 474 nm, f = 0 Excited state 3: 2.80 ev, 444 nm, f = 0 Excited state 1: 2.49 ev, 498 nm, f = 0 Excited state 2: 2.73 ev, 454 nm, f = 0 Excited state 3: 2.73 ev, 454 nm, f = 0 Excited state 1: 2.61 ev, 476 nm, f = 0 Excited state 2: 2.86 ev, 434 nm, f = 0 Excited state 3: 2.94 ev, 422 nm, f = 0 a The molecular structures TQB-TB and a-qd-tb are not stable in the ground state and thus we could not find the stationary point of their S 0 form. The optimized structure for TQB-TB was identical to that of TQB-TA. 8

9 Table S3. Calculated adiabatic excitation energies. Calculated excited-state S 1 and T 1 energy, the first vertical excitation energy (VEE), emission wavelength, oscillator strength (f) and ΔE ST for TQB and a-qd at the B3LYP/6-31++G(d,p) level Structure S 1 -adiabatic [ev] S 1 geometry [ev] TQB-TA TQB-TB TQB-TC TQB-TD a-qd-ta a-qd-tb VEE 3.27 ev 380 nm f = ev 537 nm f = ev 518 nm f = ev 386 nm f = ev 664 nm f = k f [s 1 ] a T 1 -adiabatic [ev] S 1 geometry [ev] a-qd-tb geometry b VEE 2.72 ev 456 nm f = ev 666 nm f = ev 600 nm f = ev 537 nm f = ev 865 nm f = 0 a The fluorescence rate constant, k f (s 1 ), was calculated by using Einstein s emission transition probability equation: 11 = /1.5, where is fluorescence wavenumber and f is the oscillator strength. b The molecular structure a-qd-ta is not stable in the ground state and thus we could not find the stationary point of their S 1 form. The optimized structure for a-qd-ta was identical to that of a-qd-tb. ΔE ST [ev] Figure S4. 3D coutour maps of calculated 2D PES plots. (a) PES of the first excited single state S 1. (b) PES of the first excited triplet state T 1. (c) PES of the ground state S 0. Symbols: star = TQB-TA, circle = TQB-TB, triangle = TQB-TC. 9

10 Figure S5. Natural transition orbitals and overlap integrals of hole and electron distributions. (a) The S 1 of TQB-TA. (b) The T 1 of TQB-TA. (c) The S 1 of TQB-TB. (d) The T 1 of TQB-TB. Figure S6. UV-Vis absorption and PL spectra. (a) UV-Vis (dashed lines) and PL (solid lines) spectra for TQB-doped films (ca. 10 wt%) of DPEPO, PPT, mcbp, CBP, and CzSi. (b) Magnified PL spectra. 10

11 Table S4. Photophysical properties of TQB in solution, crystal, neat film, doped film (ca. 10 wt%) under air or Ar λ abs [nm] a λ PL [nm] a Φ PL with O 2 [%] b Φ PL under Ar [%] b τ p [ns] c τ d [μs] c Calculation In DMF 323, 353, In THF 322, 352, In Toluene 325, 354, Single crystals Neat film 318, 364, Doped in DPEPO 323, 360, Doped in PPT 318, 331, 362, Doped in mcbp 331, 344, 362, Doped in CBP 331, 344, Doped in CzSi 331, 346, 361, a Measured in ambient conditions. b Absolute PL quantum yield (Φ PL ) evaluated using an integrating sphere. c PL decay lifetime of prompt (τ p ) and delayed (τ d ) components. Measured in oxygen-free solution or films at room temperature. Doped films were encapsulated in a glove box. Single crystals were measured in ambient conditions. Figure S7. PL transient decay spectra of TQB. (a) PL decay in an O 2 -free toluene, THF, and DMF. IRF is the instrument response function. (b) PL decay in crystals at room temperature. 11

12 Figure S8. UV-Vis absorption and PL spectra of a-qd. UV-Vis (dashed lines) and PL (solid lines) spectra in solution, DFT calculations, and crystal form (excitation spectrum is displayed instead of UV-Vis absorption spectrum for crystal form). Table S5. Photophysical properties of a-qd. Properties in solution, crystal, neat film, and doped film under air or Ar λ abs [nm] a λ PL [nm] a Φ PL with O 2 [%] b Φ PL under Ar [%] b τ p [ns] c τ d [μs] c Calculation In DMF 319, 334, 350, , In THF 316, 359, 388, In Toluene 316, 356, Single crystals a Measured in ambient conditions. b Absolute PL quantum yield (Φ PL ) evaluated using an integrated sphere. c PL decay lifetime of prompt (τ p ) and delayed (τ d ) components. Measured in oxygen-free solution at room temperature. Single crystals were measured in ambient conditions. Figure S9. PL transient decay spectra of a-qd. (a) PL decay in an O 2 -free THF. (b) PL decay in crystals at room temperature. 12

13 Table S6. Photophysical properties of temperature dependence for a TQB-doped film of DPEPO under vacuum Φ p [%] Φ d [%] 1/k p [ns] 1/k d [μs] Figure S10. Transient PL characteristics of a TQB-doped film of DPEPO. (a) Transient PL decay at 300 K. (b) Streak image and PL spectra were resolved into prompt (black) and delayed components (red). Each dot corresponds to the photon intensity of PL. 13

14 Figure S11. Temperature dependence of PL quantum efficiencies (Φ PL ) for a TQB-doped film of DPEPO. Lines and symbols: total emission = black square, prompt emission = red triangle, and DF = blue circle. The prompt and delayed emission are resolved by combining the absolute PL efficiency estimated by an integrating sphere photoluminescence measurement system at room temperature and the temperature dependence of the PL decay curves. The prompt emission increases with decreasing temperature because of suppression of non-radiative decay. Figure S12. PL decay of TQB neat film. (a) Temperature dependence of transient PL decay for a TQB neat film. (b) PL spectra at 6 K (no delayed emission), and at 300 K resolved into prompt and delayed emission 14

15 Figure S13. DF intensity dependence on laser fluence for a TQB-doped film of DPEPO. The sample was excited by 337 nm N 2 gas laser at room temperature. The data are fitted by a power law. Figure S14. Arrhenius plot of the reverse ISC rate from the triplet to the singlet state. k ISC set to s 1. Figure S15. Cyclic voltammograms for TQB. The neat film on an ITO electrode with 0.1 M solution of Bu 4 NClO 4 in acetonitrile at room temperature (Fc/Fc + = V). The oxidation potential was V (irreversible) and the reduction potential was 2.21 V (reversible) vs Fc/Fc +. 15

16 Figure S16. Photoelectron yield spectroscopy measurements of TQB. The ionization potential for a neat film measured with a Riken Keiki AC-3 P O O O P N N Si Si N DPEPO mcbp N N N N O P O P N N CzSi TCTA S PPT CBP N N Figure S17. Energy levels diagram of host materials and TQB and chemical structure of all OLED materials. TAPC 16

17 Figure S18. PL and EL spectra for TQB-doped films (ca. 10 wt%). (a) DPEPO as host. (b) PPT as host. (c) mcbp as host. (d) CBP as host. (e) CzSi as host. Table S7. TQB-based OLED characteristics a Device A B C D E Host DPEPO PPT mcbp CBP CzSi λ EL [nm] V on [V] L max [cd m 2 ] η c [cd A 1 ] η ext [%] a Abbreviations: λ EL = electroluminescence emission maximum, V on = turn-on voltage at 1 cd m 2, L max = maximum luminance, η c = maximum current efficiency, η ext = maximum external EL quantum efficiency (at L > 1 cd m 2 ), DPEPO = bis[2-(diphenylphosphino)phenyl]ether oxide, PPT = 2,8-bis(diphenylphosphoryl)dibenzo[b,d]- thiophene, mcbp = 3,3'-bis(carbazol-9-yl)biphenyl, CBP = 4,4'-bis(carbazol-9-yl)biphenyl, CzSi = 9-(4-tert- butylphenyl)-3,6- bis(triphenylsilyl)-9h-carbazole 17

18 Figure S19. The computationally calculated radical states. (a) Cation and (b) anion radical energies for TQB calculated at the B3LYP/6-31++G(d,p). Table S8. Calculated cation and anion radical energies for TQB. The DFT at the B3LYP/6-31++G(d,p) level Structure E + * (CEonNG) [ev] a E + (CG) [ev] b E* (NEonCG) [ev] c E * (AEonNG) [ev] d E (AG) [ev] e E* (NEonAG) [ev] f TQB-TA TQB-TB TQB-TC TQB-TD a Cation radical energy based on neutral geometry. b Cation radical ground state. c Neutral energy based on cation radical geometry. d Anion radical energy based on neutral geometry. e Anion radical ground state. f Neutral energy based on anion radical geometry. 18

19 Methods S4. Angular dependent PL measurements Thin films of TQB doped in each host matrix (15 nm thick, 10 wt%) were fabricated on pre-cleaned glasses substrates by vapor deposition and encapsulate with a coverslip under nitrogen atmosphere. The sample was attached to a half cylinder prism with a matching oil, and an excitation cw laser with a wavelength of 375 nm and a power of less than 20 mw was irradiated on the films. Through a 410 nm cut-off filter, a polarizer, and a collimating lens, photoluminescence (PL) intensity in a transverse magnetic mode was detected by a monochromator (PMA-11, Hamamatsu Photonics). The PL intensities were acquired in each out-of-plane angle from 0 (vertical to the substrate surface) to 90 (horizontal to the substrate surface) with a step of 1. The obtained radiation patterns were analyzed by a commercial software package (setfos 3.4, Fluxim). Figure S20. Radiation patterns from angular dependent PL measurements. 15-nm-thick films of TQB doped in each host matrix. 19

20 Table S9. Materials Reagents CAS No. Supplier, code and Grade 1,3,5-Tribromobenzene Tokyo Kasei Co., Ltd., T0347, >98.0% 1,3-Dibromobenzene Tokyo Kasei Co., Ltd., D0169, >97.0% Anthranilic acid Tokyo Kasei Co., Ltd., A0497, >99.0% Potassium carbonate WAKO Chemical Industries, , >99.5% Copper powder WAKO Chemical Industries, , >99.5% Copper(I) chloride WAKO Chemical Industries, , >95.0% Copper (II) acetate monohydrate WAKO Chemical Industries, , >99.0% 1-Pentanol WAKO Chemical Industries, , >98.0% Acetic acid WAKO Chemical Industries, , >99.7% Polyphosphoric acid Merck Millipore Corporation, , % OLED Materials CAS No. Supplier DPEPO Synthesized PPT Synthesized mcbp Synthesized CBP Synthesized CzSi Lumtec, LT-N484 TAPC Lumtec, LT-N137 TCTA Jilin OLED Material Tech 20

21 Table S10. Instrumentas Instruments Brands and Types Conditions Sublimation ALS technology Three-zone sublimation apparatus Elemental Analyses Yanaco MT-5 CHN corder MS Waters 3100 Mass Spectrometer Direct probe ionization, ASAP-MS NMR Bruker AVANCE III 500 MHz Chemical shifts were calibrated to the corresponding spectrometer deuterated solvents FT-IR JASCO FT/IR-6100 KBr disc method TG-DTA Bruker TG-DTA 2400SA, Under a N 2 atmosphere or 1 Pa with a heating rate of 10 C per minute Asahi spectra MAX-303 Xenon light source with a band pass-filter ( Photodegradation Hamamatsu Photonics nm, 10 mw cm 2 maintained by a feedback control a photonic multichannel unit) analyzer PMA-12 Scan = 20 ms, acquisition interval = 20 s UV-Vis PL PL quantum Yield Transient photoluminescence decay CV/DPV Photoelectron yield spectroscopy (PYS) Surface profiler XRD UV/ozone Perkin-Elmer Lambda 950-PKA UV vis spectrophotometer Horiba Jobin Yvon FluoroMax- 4 Hamamatsu Photonics Quantaurus-QY C Hamamatsu Photonics Quantaurus-Tau C Hamamatsu Photonics Streak camera C4334 equipped with Usho N 2 gas laser KEN-X and Iwatani Industrial Gases, cryostat CRT BAS 608D + DPV Electrochemical system Riken Keiki, AC-3 Bruker Dektak XT Rigaku Ultima IV diffractometer Nippon Laser & Electronics Lab. NL-UV253 The light source consisted of Deuterium (D2) and Tungsten Iodide (50W) lamps for the ultraviolet and visible regions. the excitation wavelength was set to the absorption maximum Absolute PL quantum yield Solution samples Film samples under vacuum conditions The excitation source: λ = 337 nm, pulse width 500 ps, repetition rate = 20 Hz Supporting electrolyte: tetrabutylammonium perchlorate (TBAP) (0.1 M) in acetonitrile Working electrode: an ITO, Auxiliary electrode: a platinum wire, Reference electrode: an Ag/AgNO 3. Calibration: ferrocenium-ferrocene (Fc/Fc + ) as a standard. Scan rate: 100 mv s 1 for cyclic voltammograms. in air A tip radius of 12.5 μm and a scan resolution of μm/point 40 kv and 40 ma using CuKα radiation 15 min 21

22 Data S1. NMR spectra 1 H-NMR spectrum (500 MHz, DMSO-d 6, 300 K) 13 C-NMR spectra (125 MHz, DMSO-d 6, 300 K) 13 C-NMR-APT spectra (125 MHz, DMSO-d 6, 300 K) 22

23 1 H-NMR spectrum (500 MHz, DMSO-d 6, 393 K) 1 H-NMR spectrum (500 MHz, DMSO-d 6, 300 K) 23

24 H N O O N H Quinacridone (QD) 1 H-NMR spectrum (500 MHz, DMSO-d 6, 300 K) 24

25 Data S2. FT-IR spectra 25

26 Table S11. Optimized geometry for the S 0 of TQB-TA at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C N O C O C O C H N H C H C H C H N H C H C H C H C H C H C H C H C H C H The molecular structure TQB-TB is not stable in the ground state and thus we could not find the stationary point of its S 0 form. The optimized structure for TQB-TB was identical to that of TQB-TA. 26

27 Table S12. Optimized geometry for the S 0 of TQB-TC at the B3LYP/6-31++G(d,p) level C C C N C C C C C C C C C O C O C O N H C H C H C H C H C H C H C H N H C H C H C H C H C H C H Table S13. Optimized geometry for the S 0 of TQB-TD at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C N O C O C O C H N H C H C H C H N H C H C H C H C H C H C H C H C H C H

28 Table S14. Optimized geometry for the S 1 state of TQB-TA at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H Table S15. Optimized geometry for the S 1 state of TQB-TB at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H

29 Table S16. Optimized geometry for the S 1 state of TQB-TC at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H Table S17. Optimized geometry for the S 1 state of TQB-TD at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C N O C O C O C H N H C H C H C H N H C H C H C H C H C H C H C H C H C H

30 Table S18. Optimized geometry for the T 1 state of TQB-TA at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H Table S19. Optimized geometry for the T 1 state of TQB-TB at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H

31 Table S20. Optimized geometry for the T 1 state of TQB-TC at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H Table S21. Optimized geometry for the T 1 state of TQB-TD at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C N O C O C O C H N H C H C H C H N H C H C H C H C H C H C H C H C H C H

32 Table S22. Optimized geometry for the M + of TQB-TA at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C N O C O C O C H N H C H C H C H N H C H C H C H C H C H C H C H C H C H Table S23. Optimized geometry for the M + of TQB-TB at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H

33 Table S24. Optimized geometry for the M + of TQB-TC at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C C C C O C O N H C H C H C H C H O H N H C H C H C H N H C H C H C H C H Table S25. Optimized geometry for the M + of TQB-TD at the B3LYP/6-31++G(d,p) level C C C C C C C C C C C C N O C O C O C H N H C H C H C H N H C H C H C H C H C H C H C H C H C H