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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)

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Synthesis of Tetraaryl Diazachrysenes by the Povarov Reaction and π Extension To Construct a Condensed Azaperylene MotifSynthesis of Tetraaryl Diazachrysenes by the PovarovReaction and π Extension To Construct a CondensedAzaperylene MotifYuanrong Shan,[a] Takeshi Yasuda,[b] Takaki Kanbara,[a] and Junpei Kuwabara*[a, c]Incorporating nitrogen into carbon-based materials can signifi-cantly modify their electronic properties. A comprehensiveunderstanding of the structural and physical characteristics ofaza-polycyclic aromatic hydrocarbons (aza-PAHs) is crucial fordeveloping innovative materials. In this study, four aza-PAHswere synthesized using a combination of the Povarov reactionand intramolecular cyclization reaction by direct C� H arylation.The synthesized compounds were evaluated in terms of thecrystal structure, photophysical properties, frontier energylevels, and hole-blocking properties in organic light-emittingdiode (OLED). The intramolecular cyclization by direct C� Harylation afforded a condensed azaperylene molecule thatexhibited long-wavelength absorption and emission, attributedto the high HOMO level resulting from π-extension.IntroductionAza-polycyclic aromatic hydrocarbons (aza-PAHs) are known fortheir unique optical and semiconducting properties.[1–6] Theintroduction of nitrogen atoms lowers the frontier orbitalenergy level of polycyclic aromatic hydrocarbons, enhancingtheir stability against oxidative degradation.[7–10] These featuresmake aza-PAHs promising candidates for optoelectronic appli-cations such as organic field-effect transistors (OFETs)[11–14] andorganic light-emitting diodes (OLEDs).[15–22] Various syntheticstrategies have been developed for aza-PAH production.[23–25]Recently, the Povarov reaction has been employed for thesynthesis of aza-PAHs.[26–29] Initially used for synthesizingquinoline derivatives from aromatic amines, aldehydes, andalkenes (or alkynes).[30,31] Our group previously reported doubleand triple Povarov reactions involving aromatic diamines andtriamines to obtain phenanthroline and triazatriphenylenederivatives, respectively.[26–28] Based on the previous results, weanticipated that the Povarov reaction of 1,5-naphthalenedi-amine would synthesize diazachrysene derivatives with ex-tended π-conjugation (Figure 1 and Scheme 1). Chrysene, theparent skeleton of diazachrysene, is known for its high charge-carrier mobility and has been utilized in OFETs and OLEDs.[32–35]Incorporating nitrogen atoms into chrysene is anticipated toenhance its electron-transporting properties by lowering theenergy levels. Azachrysene derivatives have been synthesizedby several methods, including the Conrad–Impah reaction,[36]one-pot multicomponent reaction,[37] and photocatalyticsynthesis.[38] On the other hand, intramolecular cyclizationreactions, commonly used for π-conjugation extension, havebeen successful in producing new materials.[39–45] We hypothe-sized that the intramolecular cyclization of azachrysene wouldyield π-extended aza-PAHs. In general, intramolecular cycliza-tion reactions are conducted using oxidative aromaticcoupling,[46–48] alkali-metal-mediated reduction coupling,[49,50] ortransition-metal-catalyzed coupling reactions.[41,51–53][a] Y. Shan, T. Kanbara, J. KuwabaraInstitute of Pure and Applied Sciences, University of Tsukuba, 1–1–1Tennodai, Tsukuba, Ibaraki 305–8573, JapanE-mail: kuwabara@ims.tsukuba.ac.jp[b] T. YasudaResearch Center for Macromolecules and Biomaterials, National Institute forMaterials Science (NIMS), 1–2–1 Sengen, Tsukuba, Ibaraki 305–0047, Japan[c] J. KuwabaraTsukuba Research Center for Energy Materials Science (TREMS), Institute ofPure and Applied Sciences, University of Tsukuba, 1–1–1 Tennodai, Tsukuba,Ibaraki 305–8573, JapanSupporting information for this article is available on the WWW underhttps://doi.org/10.1002/ajoc.202400625© 2025 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbH. This is an open access article under the terms of the CreativeCommons Attribution Non-Commercial NoDerivs License, which permits useand distribution in any medium, provided the original work is properly cited,the use is non-commercial and no modifications or adaptations are made.Figure 1. Top row: structures of chrysene and diazachrysene. Bottom row:synthetic strategy for a condensed azaperylene molecule.Wiley VCH Freitag, 28.02.20252503 / 392089 [S. 391/397] 1Asian J. Org. Chem. 2025, 14, e202400625 (1 of 7) © 2025 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbHResearch Articledoi.org/10.1002/ajoc.202400625www.asianjoc.orghttp://orcid.org/0000-0003-4652-9105http://orcid.org/0000-0002-6034-1582http://orcid.org/0000-0002-9032-5655https://doi.org/10.1002/ajoc.202400625www.asianjoc.orghttp://crossmark.crossref.org/dialog/?doi=10.1002%2Fajoc.202400625&domain=pdf&date_stamp=2025-01-20Each method offers distinct advantages for tailoring theoptoelectronic properties of these materials. In intramolecularcyclization reactions of aza-PAHs, oxidative aromatic coupling isunsuitable due to their high oxidation potentials, while alkali-metal-mediated reduction reactions require harsh reactionconditions. Therefore, transition-metal-catalyzed coupling reac-tions represent the most viable approach. In this study, weemployed an intramolecular direct C� H arylation reaction,[53–58]which requires only halogen groups for bond formation.Gorodetsky et al. reported the utility of this method insynthesizing nitrogen-containing rubicene and tetrabenzopen-tacene derivatives.[41] The primary objective of this study was tosynthesize tetraphenyl-4,10-diazachrysene derivatives by thePovarov reaction and elucidate their physical properties. Asecondary objective was to synthesize and characterize acondensed azaperylene molecule through the intramolecularcyclization of a diazachrysene derivative with Br substituentsusing a direct arylation reaction. In this study, we present thesynthesis, physical properties, and electronic structure of aza-PAHs with extended π-conjugation.Results and DiscussionSynthesisTo synthesize 1,3,7,9-tetraphenyl-4,10-diazachrysene (1a), thedouble Povarov reaction was performed under previouslyreported conditions (Scheme 1).[26] The initial reaction between1,5-naphthalenediamine and benzaldehyde, catalyzed by aceticacid, yielded a diimine intermediate (Figure S1, SupportingInformation). Without isolating this intermediate, the reactionwith phenylacetylene was subsequently conducted in thepresence of BF3·OEt2 and DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone). After purification by Soxhlet extraction, thetarget product 1a was obtained in a 68% yield. The structure of1a was confirmed using 1H NMR spectroscopy, mass spectrom-etry, and elemental analysis (Figure S2). Similarly, a 3,5-difluor-ophenyl-substituted diazachrysene derivative (1b) was synthe-sized to compare physical properties. The solubility of 1b wasnotably lower than that of 1a in common organic solvents suchas chloroform and toluene. A bromonaphthalene-substituteddiazachrysene derivative (1c) was designed for intramolecularcoupling, and t-Bu groups were introduced to the aryl groupsto improve solubility. Compound 1c was prepared in a 53%yield using the same method. Intramolecular direct arylationwas investigated to optimize reaction conditions, yielding thetarget compound 2 in a 36% yield (Scheme 1b). This is astraightforward method for the synthesis of aza-PAHs withextended π-conjugation. As the Povarov reaction[31] and thedirect arylation reaction[54–59] are highly functional grouptolerant, it is expected that a variety of related compounds canbe synthesized using this method. Due to its high thermalstability, compound 2 was purified using Soxhlet extractionfollowed by sublimation at 350 °C.Single-Crystal X-Ray Structure AnalysisThe molecular structure of 1a was determined using single-crystal X-ray diffraction (Figure 2). The analysis revealed a highlyplanar diazachrysene core. The phenyl group (α) adjacent to thenitrogen exhibited a dihedral angle of 33.9° relative to thediazachrysene core, with the other phenyl group (β) having alarger dihedral angle of 51.7°, likely due to steric hindrancebetween the C� H groups of the β phenyl group and thediazachrysene core. The shortest distance between diazachry-sene cores was 3.539 Å, indicating π-π stacking interactions inthe crystal.[60,61] Compared to the π–π stacking observed intetraphenyl-1,7-phenanthroline, synthesized similarly in a pre-Scheme 1. (a) Synthesis of 4,10-diazachrysene derivatives by the Povarov reaction. (b) Synthesis of a condensed azaperylene molecule by direct arylation.Wiley VCH Freitag, 28.02.20252503 / 392089 [S. 392/397] 1Asian J. Org. Chem. 2025, 14, e202400625 (2 of 7) © 2025 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbHResearch Article 21935815, 2025, 3, Downloaded from https://aces.onlinelibrary.wiley.com/doi/10.1002/ajoc.202400625 by National Institute For, Wiley Online Library on [17/03/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensevious study,[26,27] 1a demonstrated a greater degree of centralunit overlap due to the large π conjugation of diazachrysene(Figure S7 and S8). The effective π–π stacking interactions in 1aare reminiscent of smooth carrier transport.Physical PropertiesUV-vis absorption and emission spectra were measured toinvestigate the physical properties of the diazachrysene deriva-tives (1a, 1b) and condensed azaperylene molecules (2).Figure 3 shows the spectra for solutions and films prepared byvacuum deposition. The photophysical properties of 1a and 1bwere found to be similar. The highest occupied molecularorbital (HOMO)-lowest unoccupied molecular orbital (LUMO)gap for both compounds is 3.03 eV, which is narrower than thegap observed in tetraphenyl-1,7-phenanthroline (3.55 eV) (Fig-ure S7).[27] This narrowing is attributed to the extended π-conjugation of the diazachrysene core. Compound 2 displayeda redshift in both its maximum absorption wavelength (λmax)and maximum emission wavelength (λem) compared to 1a, 1b,and 1c (Figures 3 and S14). The π-extension achieved viaintramolecular cyclization reaction is responsible for this redshift.[43–45] A previously reported analog without nitrogen atoms(Figure S9) exhibited a λem of 534 nm, which is similar to that ofcompound 2 (544 nm).[50] This similarity suggests that the long-wavelength emission of compound 2 is likely due to theconjugated structure of its core. In addition, a significant redshift was observed especially in the thin film state, probablydue to strong π–π stacking interaction resulting from theextended π-conjugation. The maximum emission wavelength of2 reached 697 nm. Photoluminescence quantum yields (PLQYs)in the thin film state are summarized in Table 1. The reasoncompound 2 has the lowest PLQY is due to the energy gap law,where a smaller band gap results in a lower PLQY.[62] The PLQYof 1b is smaller than that of 1a because, as observed in theAFM image in Figure S12, the stronger aggregation tendency of1b leads to aggregation-induced quenching.[63] Although 1aand 1b exhibited similar photophysical properties, their energylevels differed significantly. The electron-withdrawing effect ofthe F substituents in 1b resulted in lower HOMO and LUMOFigure 2. Molecular structure and packing diagrams of 1a.Figure 3. a: UV-vis absorption spectra of 1a, 1b, and 2 (in toluene, 5.0×10� 6 M); b: UV-vis absorption spectra of 1a, 1b, and 2 (film state); c:Photoluminescence spectra (in toluene, 5.0×10� 6 M); d: Photoluminescence spectra (film state).Wiley VCH Freitag, 28.02.20252503 / 392089 [S. 393/397] 1Asian J. Org. Chem. 2025, 14, e202400625 (3 of 7) © 2025 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbHResearch Article 21935815, 2025, 3, Downloaded from https://aces.onlinelibrary.wiley.com/doi/10.1002/ajoc.202400625 by National Institute For, Wiley Online Library on [17/03/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licenseenergy levels than 1a. However, since both the HOMO andLUMO levels were affected similarly, the optical HOMO-LUMOgaps remained comparable in 1a and 1b. The HOMO andLUMO levels of a phenyl-substituted chrysene have beenreported to be � 5.79 and � 2.53 eV, respectively (Figure S10).[64]Compound 1a had lower HOMO and LUMO levels than thereference compound, revealing the effect of nitrogen incorpo-ration. The HOMO level of compound 2 was higher than that ofcompound 1a, though their LUMO levels were comparable.This elevated HOMO level is responsible for the narrow opticalband gap in compound 2. The high HOMO level of compound2 is further discussed in the density functional theory (DFT)calculations section.DFT CalculationTo investigate the electronic structures of compounds 1a, 1b,and 2, DFT calculations were performed at the B3LYP/6–31G(d)level of theory. The calculated HOMO of 1a and 2 are shown inFigure 4. For compound 2, the HOMO was also distributed atsites extended by the intramolecular cyclization. In contrast, theHOMO of 1a was not distributed to the phenyl groups, likelydue to the significant twisting of the phenyl group, which wasalso observed in its crystal structure (Figure 2, β phenyl group).The aromaticity of 2 was evaluated using nucleus-independentchemical shift (NICS) calculations (Figure 5).[65,66] The resultsshowed that ring b exhibited low aromaticity, consistent withobservations for perylene. In addition, the 1H NMR chemicalshifts of compound 2 and perylene showed high similarity(Figure S15). Based on these results, compound 2 can beviewed as a nitrogen-containing perylene derivative with acondensed structure sharing one edge.Evaluation as a Hole-Blocking Material in OLEDCompounds 1a and 1b were evaluated as hole-blockingmaterials in OLED devices due to their relatively low HOMOlevels and the possibility of large-scale synthesis (Figure 6).OLEDs with identical device configurations to those in previousstudies were fabricated to enable direct performance compar-isons with previously synthesized compounds (see Experimentalsection for details). The OLED device containing 1a exhibitedan external quantum efficiency (EQE) of 1.43%, whereas thedevice containing 1b did not function as expected. The failureof the device with 1b was attributed to the inability of thecompound to form a uniform film due to its high cohesion(Figure S12). The high cohesion of 1b was also confirmed in thelower solubility in toluene (c=1.1×10� 5 M) than 1a (c=4.2×10� 4 M). The EQE of the device without 1a showed an EQEof only 0.32%,[26,27] confirming that 1a functioned as a hole-blocking material. The EQE value of the device with 1a (1.43%)was lower than that of the device containing 1,7-phenanthro-line derivative (2.4%).[26,27] The higher HOMO level of 1a(� 6.03 eV) compared to the 1,7-phenanthroline derivative(� 6.38 eV) likely accounts for its low performance of 1a as ahole-blocking material. While it was expected that the extendedπ-conjugation of diazachrysene would improve device perform-ances through improved carrier mobility, the HOMO levelTable 1. Physical properties of 4,10-diazachrysene derivatives.Solution state [a] Thin-film stateλabs/nm λem/nm λabs/nm λem/nm PLQY/% [b] Eg, opt/eV[c] HOMO/eV [d] LUMO/eV [e]1a 388 395 394 457 19 3.03 � 6.03 � 3.001b 387 395 394 461 13 3.03 � 6.42 � 3.392 496 533 544 521 563 697 2 2.07 � 5.04 � 2.97[a] in toluene, 5.0×10� 6 M. [b] Photoluminescence Quantum Yield (PLQY). [c] Obtained from the absorption edge. [d] Obtained by photoelectron yieldspectroscopy. [e] ELUMO = Eg,opt + EHOMO.Figure 4. Highest occupied molecular orbital (HOMO) of compounds 1a and2, obtained by density functional theory (DFT) calculation at the B3LYP/6–31G(d) level of theory.Wiley VCH Freitag, 28.02.20252503 / 392089 [S. 394/397] 1Asian J. Org. Chem. 2025, 14, e202400625 (4 of 7) © 2025 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbHResearch Article 21935815, 2025, 3, Downloaded from https://aces.onlinelibrary.wiley.com/doi/10.1002/ajoc.202400625 by National Institute For, Wiley Online Library on [17/03/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensesignificantly influenced the overall efficiency of the deviceperformance.ConclusionsIn this study, four aza-PAHs were synthesized by the Povarovreaction and intramolecular cyclization reaction employingdirect C� H arylation. Single crystal X-ray structure analysis of1,3,7,9-tetraphenyl-4,10-diazachrysene (1a) revealed the highplanarity of the diazacrylene backbone and the presence of π–πstacking. Compound 1a exhibited good film-forming propertiesand acted as a hole-blocking material in OLEDs. The intra-molecular cyclization of the diazachrysene derivative with Brsubstituents by direct arylation reaction resulted in theformation of π-extended aza-PAHs bearing 10 fused benzenerings. Due to its large π-conjugation, this compound displayedlong-wavelength absorption and emission, with a maximumemission wavelength of 697 nm in the film state. DFTcalculations were used to estimate the electronic structure,demonstrating that the compound could be regarded as afused ring of perylene containing nitrogen. The condensedazaperylene motif represents a novel structural configurationamong aza-PAHs. This study provides a fundamental under-standing of the synthesis of π-extended aza-PAHs and theirstructure-property relationships, contributing to for the designfor organic optoelectronic materials.Experimental SectionSynthesis of 1aA mixture of 1,5-diaminonaphthalene (475 mg, 3.00 mmol), benzal-dehyde (637 mg, 6.00 mmol) and acetic acid (1 drop) in driedethanol (15 mL) was stirred at 78 °C for 2 h under nitrogenatmosphere. After the reaction, volatiles were removed undervacuum. The phenylacetylene (988 μL, 9.00 mmol), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 1498 mg, 6.60 mmol), BF3·OEt2(889 μL, 7.20 mmol), and dried toluene (30 mL) were added to themixture. The reaction mixture was stirred at 90 °C for 72 h undernitrogen atmosphere. After the reaction, toluene and BF3·OEt2 wereremoved under vacuum at 60 °C. The crude product was transferredto a Soxhlet extractor and washed with methanol for 9.5 h andthen acetone for 2 h at the reflux temperature. The product wasextracted with CHCl3 at the reflux temperature. After the removal ofCHCl3, light yellow solid (1a) was obtained (1065 mg, yield 68%).The analytically pure sample was obtained by sublimationpurification. 1H NMR (400 MHz, CDCl3) δ=9.61 (d, 1H, J=8.8 Hz),8.40 (d, 2H, J=7.2 Hz), 8.16 (d, 1H, J=9.2 Hz), 8.04 (s, 1H), 7.67 (d,2H, J=6.4 Hz), 7.56 (m, 6H). Anal. Calcd. for C40H26N2: C, 89.86; H,4.90; N, 5.24; Found: C, 89.69; H, 4.85; N, 5.21. MALDI-TOF-MS Calcd.for C40H26N2 (M+) 534, Found 534.1b: Light yellow solid (804 mg, yield 44%). 1H NMR (600 MHz,CDCl2CDCl2, 373 K) δ=9.54 (d, 1H, J=9.0 Hz), 8.13 (d, 1H, J=9.6 Hz), 7.91 (m, 3H), 7.57 (m, 5H), 6.90 (m, 1H). Anal. Calcd. forC40H22F4N2: C, 79.20; H, 3.66; F, 12.53; N, 4.62; Found: C, 79.44; H,3.62; N, 4.79.1c: Light yellow solid (1024 mg, yield 53%). 1H NMR (600 MHz,CDCl3) δ=9.52 (d, 1H, J=9.0 Hz), 8.30 (d, 2H, J=9.0 Hz), 8.03 (dd,1H, J=1.2, 8.4 Hz), 8.05 (s, 1H), 8.04 (dd, 1H, J=0.8, 5.2 Hz), 7.76(dd, 1H, J=1.3, 7.3 Hz), 7.67 (t, 1H, J=7.6 Hz), 7.53 (dd, 1H, J=1.4,7.0 Hz), 7.57 (d, 1H, J=9.0 Hz), 7.54 (d, 2H, J=8.6 Hz), 7.38 (t, 1H,J=7.8 Hz), 1.38 (s, 9H). Anal. Calcd. for C56H44Br2N2: C, 74.34; H, 4.90;Figure 5. Nucleus-independent chemical shift (NICS(1)) values (ppm) ofcompound 2 and perylene obtained by DFT calculation at the B3LYP/6–31G(d) level of theory.Figure 6. (a) Current density–luminance–voltage characteristics. (b) Externalquantum efficiency (EQE) versus current density of the OLED device withcompound 1a. Configuration: Glass/ITO/PEDOT:PSS (40 nm)/Green light-emitting spiro-copolymer (33 nm)/1a (40 nm)/LiF (1 nm)/Al (100 nm).Wiley VCH Freitag, 28.02.20252503 / 392089 [S. 395/397] 1Asian J. Org. Chem. 2025, 14, e202400625 (5 of 7) © 2025 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbHResearch Article 21935815, 2025, 3, Downloaded from https://aces.onlinelibrary.wiley.com/doi/10.1002/ajoc.202400625 by National Institute For, Wiley Online Library on [17/03/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons LicenseBr, 17.66; N, 3.10; Found: C, 74.45; H, 4.84; N, 3.01. MALDI-TOF-MSCalcd. for C56H44Br2N2: (M+) 904, Found 904.Synthesis of 2A mixture of 1c (54 mg, 0.06 mmol), Pd(OAc)2 (2.7 mg, 0.012 mmol),tricyclohexylphosphonium tetrafluoroborate (8.8 mg, 0.024 mmol),and potassium carbonate (66 mg, 0.48 mmol) in dried dimethylace-tamide (6.8 mL) was stirred at 130 °C for 72 h under nitrogenatmosphere. After the reaction, dimethylacetamide was removedunder vacuum at 60 °C. The crude product was transferred to aSoxhlet extractor and washed with methanol and n-hexane at thereflux temperature until the extracted solution exhibited nocoloration. The crude product was extracted with CHCl3 at thereflux temperature. The diluted solution of the products in CHCl3was purified by passing through silica gel. The product was isolatedby recrystallization by heating solution in o-dichlorobenzene to150 °C and returning to room temperature. The analytically puresample was obtained by sublimation purification at 350 °C. 2: darkred solid (16.2 mg, yield 36%). 1H NMR (600 MHz, CDCl2CDCl2,373 K) δ=10.11 (s, 1H), 8.63 (d, 1H, J=6.0 Hz), 8.54 (s, 1H), 8.37 (d,3H, overlap, J=7.8 Hz), 7.85 (d, 1H, J=7.2 Hz), 7.78 (d, 1H, J=9.0 Hz), 7.67 (d, 2H, J=7.8 Hz), 7.63 (t, 1H, J=6.3 Hz), 7.56 (t, 1H, J=6.9 Hz), 1.47 (s, 9H). Anal. Calcd. for C56H42N2: C, 90.53; H, 5.70; N,3.77; Found: C, 90.49; H, 5.47; N, 3.71. MALDI-TOF-MS Calcd. forC56H42N2: (M+) 742, Found 742.Fabrication and Characterization of OLEDsOLEDs were fabricated in the following configuration: ITO/PEDOT:PSS/emitting layer (Green light-emitting spiro-copolymer)/electron-transporting and hole-blocking layer (1a)/LiF/Al. The patternedindium tin oxide (ITO) glass (conductivity: 10 Ω/square) was pre-cleaned in an ultrasonic bath of acetone and ethanol and thentreated in an ultraviolet-ozone chamber. A thin layer (40 nm) ofPEDOT:PSS was spin-coated onto the ITO at 3000 rpm and air-driedat 110 °C for 10 min on a hot plate. The substrate was thentransferred to a N2-filled glove box where it was re-dried at 110 °Cfor 10 min on a hot plate. A toluene solution of Green light-emitting spiro-copolymer (4 mg/1 mL) was subsequently spin-coated onto the PEDOT:PSS surface to form the light-emitting layerwith the thicknesses of 33 nm and the light-emitting layer wasdried at 80 °C for 10 min. 1a (40 nm), LiF (1 nm) and Al (100 nm)were then deposited onto the active layer with conventionalthermal evaporation at a chamber pressure lower than 5×10� 4 Pa,which provided the devices with an active area of 2×2 mm2.Current-voltage characteristics and luminance of the OLED weresimultaneously measured using an ADCMT 6245 DC voltage currentsource/monitor (ADC CORPORATION) and an LS-100 luminancemeter (KONICA MINOLTA, INC.), respectively. The EL spectra weremeasured using an array spectrometer (MCPD-9800–311 C, OtsukaElectronics Co, Ltd.).Supporting Information SummaryElectronic Supplementary Information (ESI) available: Supple-mentary figures, computational details, and crystallographicdata in CIF. CCDC 2393382.AcknowledgementsThe authors thank the Chemical Analysis Center of theUniversity of Tsukuba for the measurements of NMR, the single-crystal X-ray diffraction, and MALDI-TOF-MS. The authors aregrateful to Riken Keiki Co. Ltd. for measurements of photo-electron yield spectroscopy using an AC-3 spectrometer. Theauthors thank Dr. A. Takai for their assistance with the massspectrometry. This work was partially supported by JSPSKAKENHI Grant Number JP22K05075, JP23K04884, IketaniScience and Technology Foundation, and JST SPRING, JapanGrant Number JPMJSP2124.Conflict of InterestsThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are availablefrom the corresponding author upon reasonable request.Keywords: Povarov reaction · Diazachrysenes · Condensedazaperylene · Hole-blocking material[1] Y. Takeda, P. Data, S. Minakata, Chem. Commun. 2020, 56, 8884–8894.[2] W. Zong, N. Hippchen, B. Dittmar, M. Elter, P. Ludwig, F. Rominger, J.Freudenberg, U. H. Bunz, Asian J. Org. Chem. 2023, 12, e202300462.[3] H. Xin, J. Li, R.-Q. Lu, X. Gao, T. M. Swager, J. Am. Chem. Soc. 2020, 142,13598–13605.[4] M. Krzeszewski, D. Gryko, D. T. Gryko, Acc. Chem. Res. 2017, 50, 2334–2345.[5] U. H. F. Bunz, Acc. Chem. Res. 2015, 48, 1676–1686.[6] U. H. Bunz, J. Freudenberg, Acc. Chem. Res. 2019, 52, 1575–1587.[7] H. Ye, D. Chen, M. 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