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## Creator

Yuanrong Shan, [Takeshi Yasuda](https://orcid.org/0000-0003-4652-9105), [Takaki Kanbara](https://orcid.org/0000-0002-6034-1582), [Junpei Kuwabara](https://orcid.org/0000-0002-9032-5655)

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[Synthesis of Tetraaryl Diazachrysenes by the Povarov Reaction and π Extension To Construct a Condensed Azaperylene Motif](https://mdr.nims.go.jp/datasets/f3a2471a-9792-425c-b7f7-e3a79a59b507)

## Fulltext

Asian Journal ofOrganic ChemistrySupporting InformationSynthesis of Tetraaryl Diazachrysenes by the PovarovReaction and π Extension To Construct a CondensedAzaperylene MotifYuanrong Shan, Takeshi Yasuda, Takaki Kanbara, and Junpei Kuwabara*Wiley VCH Freitag, 28.02.20252503 / 392089 [S. 398/398] 11  Supporting Information  Synthesis of Tetraaryl Diazachrysenes by the Povarov Reaction and π Extension To Construct a Condensed Azaperylene Motif  Yuanrong Shan,[a] Takeshi Yasuda,[b] Takaki Kanbara,[a] Junpei Kuwabara*[a][c] [a] Y. Shan, Prof. T. Kanbara, Prof. J. Kuwabara Institute of Pure and Applied Sciences  University of Tsukuba 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan [b] Dr. T. Yasuda Research Center for Macromolecules and Biomaterials, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan. [c] Prof. J. Kuwabara Tsukuba Research Center for Energy Materials Science (TREMS), Institute of Pure and Applied Sciences, University of Tsukuba 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan E-mail: kuwabara@ims.tsukuba.ac.jp  General, Measurement, and Materials. 1H NMR spectra were recorded using Bruker AVANCE-400 NMR spectrometer and AVANCE-600 NMR spectrometer. Elemental analyses were carried out using a Yanaco CHN coder MT-6 or MT-5. Crystal structure determination intensity data were collected on a Bruker SMART APEX II ULTRA with Mo K𝛼  radiation. MALDI-TOF-MS spectra were recorded on an AB SCIEX TOF/TOF (TM) 5800 system. UV-Vis absorption spectra in solution and film state were recorded on a Hitachi U-3900H and Hitachi U-3010 spectrophotometer, respectively. The photoluminescence (PL) spectra in the solution state and the thin film state were recorded Hitachi F-2700 fluorescence spectrophotometer and a JASCO FP-6500, respectively. The PL quantum yields (PLQY) of the emission were measured using a Hamamatsu Photonics C9920-02 absolute PL quantum yield spectrometer. The HOMO energy levels were estimated by photoelectron yield spectroscopy (PYS) using an AC-3 spectrometer (Riken Keiki). The surface morphology of films was examined with an atomic force microscope (AFM) (Hitachi High-Tech Corporation, AFM5100N and AFM5000II). Dry solvents were purchased from Kanto Chemical. Green light-emitting spiro-copolymer (Livilux™ SPG-01T, CAS 1430803-21-6, average Mn >100,000, EHOMO = -5.38 eV, ELUMO = -2.81 2  eV) was purchased from Sigma-Aldrich. The other reagents were purchased from Tokyo Chemical Industry Co., Ltd. (TCI), Sigma-Aldrich and FUJIFILM Wako Pure Chemical Corporation.  3  Synthesis of 1-bromo-8-ethynylnaphthalene.[S1]  A mixture of 1,8-dibromonaphthalene (2860 mg, 10.0 mmol), Pd(PPh3)4 (580 mg, 0.500 mmol), CuI (190 mg, 1.00 mmol),  trimethylsilylacetylene (1520 μL, 11.0 mmol) and triethylamine (4 mL) in dried THF (6 mL) was stirred at 65 °C for 3 h under nitrogen atmosphere. After the reaction, the crude product was extracted with CHCl3 and dried with sodium sulfate. The intermediate product with a TMS group was isolated by column chromatography on silica gel using hexane as an eluent (brown oil). To the intermediate product, potassium carbonate (2764 mg, 20.0 mmol) in methanol (30 mL) were added and stirred at r.t. for 2 h. After the reaction, the crude product was extracted with CHCl3 and dried with sodium sulfate. The product was isolated by column chromatography on silica gel using hexane as an eluent. After evaporation, 1-bromo-8-ethynylnaphthalene was obtained (1499 mg, total yield 65%, brown solid). 1H NMR (400 MHz, CDCl3) δ = 7.89 (dd, 1H, J = 1.6, 7.2 Hz), 7.84 (d, 2H, J = 7.6 Hz), 7.80 (dd, 1H, J = 0.8, 8.4 Hz), 7.42 (t, 1H, J = 7.8 Hz), 7.28 (t, 1H, J = 7.6 Hz), 3.58 (s, 1H).     4  NMR Spectroscopy Figure S1. 1H NMR spectrum of the diimine intermediate prepared from1,5-naphthalenediamine and benzaldehyde (400 MHz, CDCl3, r.t.)   Figure S2. 1H NMR spectrum of 1a (400 MHz, CDCl3, r.t.)  5     Figure S3. 1H NMR spectrum of 1b (600 MHz, CDCl2CDCl2, 373 K)     6  Figure S4. 1H NMR spectrum of 1-bromo-8-ethynylnaphthalene (400 MHz, CDCl3, r.t.)   Figure S5. 1H NMR spectrum of 1c (600 MHz, CDCl3, r.t.)     7  Figure S6. 1H NMR spectrum of 2 (600 MHz, CDCl2CDCl2, 373 K)     Figure S7. The chemical structure and energy levels of a tetraphenyl-1,7-phenanthroline. [S2]    Figure S8. Stacking structures of (a) the tetraphenyl-1,7-phenanthroline [S2] and (b) 1a in crystalline state.  8    Figure S9. The chemical structure of the reference compound. [S3]    Figure S10. The chemical structure of the reference compound. [S4]   9    Figure S11. Frontier molecular orbitals for compounds 1a, 1b and 2, orbitals by DFT calculation， at the level of B3LYP/6-31G(d).     10  1a RMS 0.6208 nm                          1b RMS 6.978 nm                        2 RMS 0.9960 nm   Figure S12.  AFM images of a vacuum-deposited film of 1a, 1b, and 2.    Figure S13. PL spectrum from the thin film of Green light-emitting spiro-copolymer (GP) and EL spectrum from GP in the OLEDs with 1a in Figure 6.    11  Figure S14. (a)UV-vis absorption and (b) photoluminescence spectra of 1c and 2 (in toluene, 5.0 × 10-6 M).   Figure S15. Chemical shift values of perylene[S5] and 2 in 1H NMR.   Table S1. Calculated frontier molecular orbitals energy for compounds 1a, 1b and 2, obtained by DFT calculation at the level of B3LYP/6-31G(d).   Eg / eV HOMO / eV LUMO / eV 1a 3.05 -5.50  -1.75  1b 3.09 -5.78  -2.04  2 2.23 -4.84  -2.34     12  Table S2. Crystallographic data of 1a.   1a CCDC No 2393382 Chemical formula C40H26N2  Formula weight 534.66 Crystal system triclinic Space group P-1 (#2) a [Å] 10.5687(6) b [Å] 11.4271(6) c [Å] 11.6197(7) Å 𝛼 [°] 87.2700 𝛽 [°] 76.9590 𝛾 [°] 89.0390 V [Å3] 1365.54(13) Z value 2 µ(MoK𝛼) [cm-1] 0.754 F000 560.00 Dcalc 1.300 crystal dimensions 0.176 x 0.096 x 0.090 No. of data 15746 No. of unique data 5990 No. of variables 379 R (I > 2.00𝜎(I)) 0.0394 R (All reflections) 0.0461 RW (All reflections) 0.1052 GOF 1.045  References [S1] S. Reimann, P.Ehlers , M. Sharif , K. Wittler, A. Spannenberg, R. Ludwig , P. Langer, Catal. Commun. 2012, 25, 142–147. [S2] S. Yamamoto, T. Yasuda, T. Kanbara, J. Kuwabara, Bull. Chem. Soc. Jpn. 2022, 95, 458–465. [S3] K. Fujishiro, Y. Morinaka, Y. Ono, T. Tanaka, L. T. Scott, H. Ito, K. Itami, J. Am. Chem. Soc. 2023, 145, 8163–8175. [S4] Y. He, W. Xu, I. Murtaza, C. Yao, Y. Zhu, A. Li, C. He, H. Meng, J. Mater. Chem. C 2018, 6, 3683–3689. [S5] E. Stammers, C. D. Parsons, J. Clayden and A. J. J. Lennox, Nat. Commun. 2023, 14, 4561–4567.