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## Creator

Ryota Iwamori, Junpei Kuwabara, [Takeshi Yasuda](https://orcid.org/0000-0003-4652-9105), Takaki Kanbara

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This is the peer reviewed version of the following article: R. Iwamori, J. Kuwabara, T. Yasuda, T. Kanbara, Molecular Design of Naphthalene- and Carbazole-Based Monomers for Regiospecific Synthesis of Poly(arylenevinylene)s via Co-Catalyzed Hydroarylation Polyaddition. Macromol. Rapid Commun. 2024, 45, 2400168, which has been published in final form at https://doi.org/10.1002/marc.202400168. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

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[Molecular Design of Naphthalene‐ and Carbazole‐Based Monomers for Regiospecific Synthesis of Poly(arylenevinylene)s via Co‐Catalyzed Hydroarylation Polyaddition](https://mdr.nims.go.jp/datasets/67cce730-53f6-4aa3-b66b-e778b5494bbd)

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Microsoft Word - Iwamori_MARC24_SI- 1 -Supporting InformationMolecular Design of Naphthalene- and Carbazole-Based Monomersfor Regiospecific Synthesis of Poly(arylenevinylene)svia Co-catalyzed Hydroarylation PolyadditionRyota Iwamori a, Junpei Kuwabara a,b, Takeshi Yasuda c and Takaki Kanbara a*a Institute of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki,305-8573, Japan.b Tsukuba Research Center for Energy Materials Science (TREMS), Institute of Pure and AppliedSciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan.c Research Center for Macromolecules and Biomaterials, National Institute for Materials Science(NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.Corresponding AuthorTakaki Kanbara* (E-mail: kanbara@ims.tsukuba.ac.jp)Table of contentsExperimental section………………………………………………………………………………2Model reactions and hydroarylation polyaddition…………………………………………………7NMR and MS spectra………………………………………………………………………………9GPC charts..………………………………………………………………………………………22DFT calculations and X-ray crystallographic data…...………………………………………...…23Optical and electronic data..………………………………………………………………………25- 2 -Experimental sectionMaterialsAll reagents from commercial sources were used without further purification, unless otherwise noted. Anhydroussolvents were purchased from Kanto Chemical. 4-Ethynyltoluene (2a), 1-phenylpyrazole (1b),4,4’-diethynylbiphenyl (7c), and 2,2’,2’’-(1,3,5-benzenetriyl)tris(1-phenylbenzimidazole) (TPBi) were purchasedfrom Tokyo Chemical Industry. Neodecanoic acid (NDA) was purchased from Wako Pure Chemical Industries.2-Phenylpyridine (1a) and 4-tert-butylphenylacetylene (2b) were purchased from Sigma Aldrich.Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS, CLEVIOS P VP AI 4083) was purchasedfrom Heraeus. The other regents were also purchased from Kanto Chemical, Tokyo Chemical Industry, and SigmaAldrich. TPBi was purified by thermal sublimination before use.2,7-Bis(4-ethynylphenyl)-9,9-bis(2-octyldodecyl)fluorene (7a), 2,7-bis(4-ethynylphenyl)-9,9-di(n-octyl)fluorene(7b), and [Cp*Co(CH3CN)3](SbF6)2 were synthesized by the same methods as our previous reports.[1]General methodsNMR spectra were recorded on a Bruker AVANCE-400 and AVANCE-600 NMR spectrometer. 1H and 13C{1H}NMR spectra were measured with CHCl3 (7.26 ppm for 1H NMR), C2HDCl4 (6.00 ppm for 1H NMR), and CDCl3(77.0 ppm for 13C NMR) as an internal reference. DFT calculations were performed by Gaussian at theB3LYP/6-31G(d) level. Crystal Structure Determination Intensity data were collected on a Bruker SMART APEXII ULTRA with Mo Kα radiation. GPC measurements were carried out on a SHIMADZU prominence GPC system equipped with polystyrene gel columns, using THF as an eluent after calibration with polystyrenestandards. MALDI-TOF-MS spectra were recorded on an AB SCIEX MALDI TOF/TOF 5800 usingtrans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) as matrix. Elemental analyseswere carried out with Yanaco CHN coder MT-6 or MT-5. UV-vis absorption spectra in solution states wererecorded on a Hitachi U-3900H or a JASCO V-630. PL spectra in solution states were recorded on a HitachiF-2700 fluorescence spectrophotometers. UV-vis absorption spectra and PL spectra for the spin-coated films wererecorded on a Hitachi U-3010 and JASCO FP-6500 spectrophotometer, respectively. PLQYs of the spin-coatedfilms were measured using a JASCO FP-6500 spectrophotometer with an integrating sphere. The HOMO energylevels were estimated by PYS using an AC-3 spectrometer (Riken Keiki). The surface morphologies of thepolymer films were observed using AFM (5100N and 5000II, Hitachi High-Tech Corporation). XRDmeasurements were performed using MiniFlex600 (Rigaku Corporation, Cu Kα radiation). High-resolution massspectroscopy (HRMS) was carried out with an APCI-Direct Probe of Bruker micrOTOF II. All of themanipulations for the reactions were performed under a nitrogen atmosphere using Schlenk techniques.Small molecular model reaction of mono-substituted benzene (Figure 1)To a stirred solution of a mono-substituted benzene (1a-1e, 0.10 mmol), 4-ethynyltoluene (2a, 26.6 μL, 0.21 mmol), and 1,3,5-trimethoxybenzene (11.2 mg, 0.067 mmol) in anhydrous THF (1.0 mL) was added[Cp*Co(CH3CN)3](SbF6)2 (3.94 mg, 0.0050 mmol) and NDA (11.4 μL, 0.060 mmol). The reaction mixture was stirred for 24 h at 30 °C under nitrogen atmosphere. A portion of the reaction mixture was sampled at 0 and 24 h.The NMR yield was calculated from the integral value of the signal for the product on the basis of the internalstandard (1,3,5-trimethoxybenzene).- 3 -Small molecular model reaction of naphthalene- and carbazole-based monomersTo a stirred solution of an aromatic monomer (0.10 mmol), 4-tert-butylphenylacetylene (2b, 37.4 μL, 0.21 mmol), and 1,3,5-trimethoxybenzene (11.2 mg, 0.067 mmol) in anhydrous THF (2.0 mL) was added[Cp*Co(CH3CN)3](SbF6)2 (3.94 mg, 0.0050 mmol) and NDA (18.9 μL, 0.10 mmol). The reaction mixture was stirred for 24 h at 30 °C under nitrogen atmosphere. A portion of the reaction mixture was sampled at 0 and 24 h.The NMR yield was calculated from the integral value of the signal for the product on the basis of the internalstandard (1,3,5-trimethoxybenzene). Isolation of the product is described below.Synthesis of 6ab (Scheme 2a)2,6-Di(1-pyrazolyl)naphthalene (5a, 52.0 mg, 0.20 mmol) was used as the aromatic monomer. The reactionmixture was diluted with CHCl3 (50 mL) and poured into NH3 solution (28% in water, 50 mL). The organic layerwas washed with NH3 solution and distilled water (100 mL x 2). The organic layer was dried over sodium sulfateand filtered through a Celite plug. The product was isolated by silica gel column chromatography using hexane :ethyl acetate (9:1 → 4:1) as an eluent. 6ab was obtained as a yellow solid in 82% yield (94.6 mg). 1H NMR (600MHz, CDCl3, r.t.): δ 8.16 (s, 2H), 7.98 (s, 2H), 7.84 (d, J = 1.7, 2H), 7.78 (d, J = 2.2, 2H), 7.38 (s, 8H), 7.11 (d, J= 16.1, 2H), 7.02 (d, J = 16.2, 2H), 6.53 (t, J = 2.1, 2H), 1.33 (s, 18H). 13C{1H} NMR (150 MHz, CDCl3, r.t.): δ151.43, 140.97, 138.11, 134.29, 132.90, 132.00, 131.88, 131.69, 126.62, 125.66, 124.58, 123.29, 106.86, 34.69,31.27. Anal. calcd. for C40H40N4: C 83.30, H 6.99, N 9.71; found: C 83.12, H 6.76, N 9.69.Synthesis of 6cb (Scheme S2)9-(2-Ethylhexyl)-3,6-di(1-pyrazolyl)carbazole (5c, 82.3 mg, 0.20 mmol) was used as the aromatic monomer. Thereaction mixture was diluted with CHCl3 (50 mL) and poured into NH3 solution (28% in water, 50 mL). Theorganic layer was washed with NH3 solution and distilled water (100 mL x 2). The organic layer was dried oversodium sulfate and filtered through a Celite plug. The product was isolated by silica gel column chromatographyusing hexane : ethyl acetate (1:0 → 4:1) as an eluent. 6cb was obtained as a yellow solid in 73% yield (106 mg).1H NMR (400 MHz, CDCl3, r.t.): δ 8.02 (s, 2H), 7.79 (s, 2H), 7.67 (s, 4H), 7.36 (s, 8H), 7.07 (d, J = 16.4, 2H),6.91 (d, J = 16.4, 2H), 6.48 (d, J = 1.9, 2H), 4.22 - 4.40 (m, 2H), 2.05 - 2.27 (m, 1H), 1.39 - 1.50 (m, 8H), 1.32 (s,18H), 0.99 (t, J = 7.2, 3H), 0.92 (t, J = 7.1, 3H). 13C{1H} NMR (100 MHz, CDCl3, r.t.): δ 151.11, 141.86, 140.40,134.44, 132.62, 132.14, 132.12, 130.45, 126.45, 125.60, 124.24, 121.97, 118.76, 106.24, 105.72, 47.51, 39.43,34.64, 31.26, 31.00, 28.87, 24.55, 23.03, 14.13, 11.00. Anal. calcd. for C50H57N5: C 82.49, H 7.89, N 9.62; found:C 82.47, H 8.03, N 9.57.Deuterium exchange experiment (Scheme 3)To a stirred solution of a naphthalene derivative (0.10 mmol) and 1,3,5-trimethoxybenzene (11.2 mg, 0.067 mmol)in anhydrous THF (2.0 mL) was added [Cp*Co(CH3CN)3](SbF6)2 (3.94 mg, 0.0050 mmol) and CD3COOD (11.4μL, 0.20 mmol). The reaction mixture was stirred for 24 h at 30 °C under nitrogen atmosphere. A portion of the reaction mixture was sampled at 0 and 24 h. The deuterium ratio was calculated from the integral value of thesignal for the product on the basis of the internal standard (1,3,5-trimethoxybenzene).- 4 -Synthesis of Paa (Scheme 4a)To a stirred solution of 5a (26.0 mg, 0.10 mmol) and 2,7-bis(4-ethynylphenyl)-9,9-bis(2-octyldodecyl)fluorene(7a, 92.8 mg, 0.10 mmol) in anhydrous THF (5.0 mL) were added [Cp*Co(CH3CN)3](SbF6)2 (3.94 mg, 0.0050mmol) and NDA (18.9 μL, 0.10 mmol). The reaction mixture was stirred for 24 h at 30 °C under a nitrogenatmosphere in the dark. Then, the reaction mixture was diluted with CHCl3 (50 mL) and poured into NH3 solution(28% in water, 50 mL). The organic layer was washed with NH3 solution and distilled water (100 mL × 2). Theorganic layer was dried over sodium sulfate and filtered through a Celite plug. The solution of CHCl3 wasconcentrated and reprecipitated into methanol. The precipitate was filtered and a polymeric product (Paa) wasobtained as a yellow solid in 96% yield (114 mg, Mn = 4.1 × 104, PDI = 3.9). 1H NMR (600 MHz, C2D2Cl4, 373K): δ 8.27 (s, 2H), 8.07 (s, 2H), 7.92 (s, 2H), 7.88 (s, 2H), 7.82 (d, J = 7.4, 2H), 7.48 - 7.77 (m, 12H), 7.20 (s, 4H),6.62 (s, 2H), 2.16 (s, 2H), 0.71 - 1.40 (m, 80H). Anal. calcd. for C85H110N4: C 85.95, H 9.33, N 4.72; found: C85.07, H 9.30, N 4.74.Synthesis of Pcb (Scheme 4b)Pcb was obtained by the same procedure as Paa.5c (41.2 mg, 0.10 mmol) and 2,7-bis(4-ethynylphenyl)-9,9-di(n-octyl)fluorene (7b, 59.1 mg, 0.10 mmol) wereused as the monomers. The reaction was carried out at 30 °C for 24 h, giving Pcb as an yellow solid in 73% yield(73.4 mg, Mn = 1.1 × 104, PDI = 2.8). The reaction was also carried out at 30 °C for 48 h, giving Pcb as a yellowsolid in 71% yield (71.4 mg, Mn = 2.3 × 104, PDI = 3.4). 1H NMR (400 MHz, CDCl3, r.t.): δ 8.10 (s, 2H), 7.86 (s,2H), 7.45 - 7.84 (m, 18H), 7.19 (d, J = 16.3, 2H), 7.06 (d, J = 16.0, 2H), 6.56 (s, 2H), 4.37 (m, 2H), 1.92 - 2.33 (m,5H), 0.63 - 1.55 (m, 44H). Anal. calcd. for C71H79N5: C 85.07, H 7.94, N 6.99; found: C 85.28, H 7.67, N 6.71.Synthesis of Pcc (Scheme S3)5c (41.2 mg, 0.10 mmol) and 4,4’-diethynylbiphenyl (7c, 20.2 mg, 0.10 mmol) were used as the monomers. Thereaction was carried out at 30 °C for 24 h, and precipitates were corrected by filtration. The obtained solid waspurified via Soxhlet extraction with methanol and tetrachloroethane. The solution of tetrachloroethane wasconcentrated and reprecipitated into n-hexane. The precipitate was filtered and a polymeric product (Pcc) wasobtained as a red solid in 75% yield (45.7 mg). 1H NMR (400 MHz, C2D2Cl4, r.t.): δ 8.08 (s, 2H), 7.84 (s, 2H),7.77 (s, 4H), 7.39 - 7.70 (m, 8H), 7.15 (d, J = 15.7, 2H), 7.03 (d, J = 15.9, 2H), 6.56 (s, 2H), 4.34 (m, 2H), 2.06 -2.30 (m, 1H), 1.24 - 1.55 (m, 8H), 0.79 - 1.11 (m, 6H).Fabrication and Characterization of OLED.OLED was fabricated in the following configuration: ITO/PEDOT:PSS/light-emitting Paa layer/electrontransporting (hole blocking) TPBi layer/LiF/Al. The patterned indium tin oxide (ITO) glass (conductivity: 10Ω/square) was precleaned in an ultrasonic bath of acetone and ethanol and then treated in an ultraviolet-ozone chamber. A thin layer (40 nm) of PEDOT:PSS was spin-coated onto the ITO at 3000 rpm and air-dried at 110 °Cfor 10 min on a hot plate. The substrate was then transferred to a N2-filled glovebox where it was redried at110 °C for 10 min on a hot plate. A chloroform solution of Paa (5 mg/1 mL) was subsequently spin-coated ontothe PEDOT:PSS surface to form the light-emitting layer (47 nm). TPBi (40 nm), LiF (1 nm), and Al (100 nm)were then deposited onto the active layer with conventional thermal evaporation at a chamber pressure lower than5 x 10−4 Pa, which provided the devices with an active area of 2 x 2 mm2. Current−voltage characteristics and - 5 -luminance of the OLED were simultaneously measured using an ADCMT 6245 DC voltage currentsource/monitor (ADC CORPORATION) and an LS-100 luminance meter (KONICA MINOLTA JAPAN, INC.),respectively. The EL spectra and the coordinates of the CIE chromaticity were measured using an arrayspectrometer (MCPD-9800-311C, Otsuka Electronics Co, Ltd.).Synthesis of 2,6-di(1-pyrazolyl)naphthalene (5a, Figure S23)[2]A solution of 2,6-dibromonaphthalene (286 mg, 1.0 mmol), pyrazole (204 mg, 3.0 mmol), Cu2O (28.6 mg, 0.20mmol), and Cs2CO3 (1.30 g, 4.0 mmol) in DMF (2.0 mL) was stirred for 24 h at 120 °C under nitrogenatmosphere. The crude mixture was dried under vacuum and dissolved in dichloromethane. The solution filteredthrough a Celite plug, and rinsed with dichloromethane. The product was isolated by silica gel columnchromatography using hexane : ethyl acetate (3:1 → 1:1) as an eluent. 2,6-di(1-pyrazolyl)naphthalene (5a) wasobtained as a white solid in 87% yield (227 mg). 1H NMR (600 MHz, CDCl3, r.t.): δ 8.15 (d, J = 1.9, 2H), 8.08 (d,J = 2.1, 2H), 7.98 (d, J = 8.8, 2H), 7.95 (dd, J = 1.9, 8.8, 2H), 7.80 (d, J = 1.3, 2H), 6.54 (t, J = 2.0, 2H). Anal.calcd. for C16H12N4: C 73.83, H 4.65, N 21.52; found: C 73.59, H 4.43, N 21.67. 5b and 5c were obtained by thesame procedure.Synthesis of 1,5-di(1-pyrazolyl)naphthalene (5b, Figure S24)1,5-Dibromonaphthalene (286 mg, 1.0 mmol) was used instead of 2,6-dibromonaphthalene. The reaction was alsocarried out at 120 °C for 24 h, giving 1,5-di(1-pyrazolyl)naphthalene (5b) as a white solid in 85% yield (221 mg).1H NMR (600 MHz, CDCl3, r.t.): δ 7.90 (d, J = 8.4, 2H), 7.87 (d, J = 1.3, 2H), 7.81 (d, J = 2.2, 2H), 7.55 - 7.62(m, 4H), 6.57 (t, J = 2.0, 2H). Anal. calcd. for C16H12N4: C 73.83, H 4.65, N 21.52; found: C 73.92, H 4.52, N21.73.Synthesis of 9-(2-ethylhexyl)-3,6-di(1-pyrazolyl)carbazole (5c, Figure S25)9-(2-Ethylhexyl)-3,6-dibromocarbazole (437 mg, 1.0 mmol) was used instead of 2,6-dibromonaphthalene. Thereaction was also carried out at 120 °C for 24 h, giving 9-(2-ethylhexyl)-3,6-di(1-pyrazolyl)carbazole (5c) as acolorless oil in 95% yield (391 mg). 1H NMR (600 MHz, CDCl3, r.t.): δ 8.37 (d, J = 1.8, 2H), 7.98 (d, J = 2.5, 2H),- 6 -7.79 - 7.87 (m, 2H), 7.77 (s, 2H), 7.45 (d, J = 8.8, 2H), 6.45 - 6.56 (m, 2H), 4.13 - 4.28 (m, 2H), 2.01 - 2.15 (m,1H), 1.17 - 1.48 (m, 8H), 0.93 (t, J = 7.4, 3H), 0.86 (t, J = 7.0, 3H). HRMS (APCI): m/z calculated for C26H30N5+[M+H+]: 412.2496, found: 412.2509.Synthesis of 2,6-bis((E)-4-tert-butylstyryl)naphthalene (8a, Figure S26)[3]To a stirred solution of 2,6-dibromonaphthalene (85.8 mg, 0.30 mmol), Pd(OAc)2 (13.5 mg, 0.060 mmol), andtris(o-tolyl)phosphine (36.5 mg, 0.12 mmol) in anhydrous DMF (1.5 mL) was added 4-tert-butylstyrene (164 μL, 0.90 mmol) and triethylamine (1.5 mL). The reaction mixture was stirred for 24 h at 80 °C under nitrogenatmosphere. The crude mixture was filtered through a Celite plug, and rinsed with toluene. The toluene solutionwas poured into water, and washed with water and brine. The organic layer was dried over sodium sulfate, andfiltered through a Celite plug. The product was isolated by silica gel column chromatography using hexane :chloroform (1:0 → 1:1) as an eluent, followed by washing with methanol and recrystallization with chloroform and hexane. 2,6-bis((E)-4-tert-butylstyryl)naphthalene (8a) was obtained as a white solid in 37% yield (49.1 mg).1H NMR (600 MHz, CDCl3, r.t.): δ 7.82 (d, J = 1.4, 2H), 7.80 (d, J = 8.5, 2H), 7.73 (dd, J = 1.3, 8.6, 2H), 7.51 (d,J = 8.4, 4H), 7.41 (d, J = 8.5, 4H), 7.23 (s, 4H), 1.35 (s, 18H). Anal. calcd. for C34H36: C 91.84, H 8.16; found: C91.68, H 8.26.Synthesis of 9-(2-ethylhexyl)-2,7-bis((E)-4-tert-butylstyryl)carbazole (8b, Figure S27)[3]To a stirred solution of 9-(2-ethylhexyl)-2,7-dibromocarbazole (131 mg, 0.30 mmol), Pd(OAc)2 (13.5 mg, 0.060mmol), and tris(o-tolyl)phosphine (36.5 mg, 0.12 mmol) in anhydrous DMF (1.5 mL) was added4-tert-butylstyrene (164 μL, 0.90 mmol) and triethylamine (1.5 mL). The reaction mixture was stirred for 24 h at 80 °C under nitrogen atmosphere. The crude mixture was filtered through a Celite plug, and rinsed with toluene.The toluene solution was poured into water, and washed with water and brine. The organic layer was dried oversodium sulfate, and filtered through a Celite plug. The product was isolated by silica gel column chromatographyusing hexane : ethyl acetate (1:0 → 4:1) as an eluent, followed by high performance liquid chromatography (HPLC) and recrystallization with chloroform and hexane.9-(2-ethylhexyl)-2,7-bis((E)-4-tert-butylstyryl)carbazole (8b) was obtained as a white solid in 36% yield (63.1mg). 1H NMR (600 MHz, CDCl3, r.t.): δ 8.01 (d, J = 8.1, 2H), 7.52 (d, J = 8.3, 4H), 7.43 - 7.46 (m, 4H), 7.41 (d, J= 8.4, 4H), 7.26 (d, J = 16.9, 2H), 7.21 (d, J = 16.2, 2H), 4.09 - 4.33 (m, 2H), 2.09 - 2.17 (m, 1H), 1.29 - 1.50 (m,8H), 1.35 (s, 18H), 0.96 (t, J = 7.4, 3H), 0.91 (t, J = 7.3, 3H). Anal. calcd. for C44H53N: C 88.68, H 8.97, N 2.35;found: C 88.65, H 9.01, N 2.22.- 7 -Model reactions and hydroarylation polyadditionTable S1. Optimization of hydroarylation reaction of 1b with 2a [a]Entry x [M] y [mol%] Conversion of 1b [%] [b] Yield of 3ba [%] [b] Yield of 4ba [%] [b]1 0.10 60 80 (49) [c] 62 182 0.05 60 97 (62) [c] 70 273 0.05 30 54 (32) [c] 45 9.14 0.05 100 96 (66) [c] 61 35[a] Reaction conditions: 1b (1.0 equiv., 0.10 mmol), 2a (2.1 equiv., 0.21 mmol), [Cp*Co(CH3CN)](SbF6)2 (5mol%), Neodecanoic acid (NDA, 30-100 mol%), and tetrahydrofuran (THF, 1.0 or 2.0 mL), 24 h under N2atmosphere at 30 °C. [b] Conversions and yields were calculated by 1H NMR analyses using1,3,5-trimethoxybenzene as an internal standard. [c] Consumption of C-H bonds adjacent to an 1-pyrazole group.Scheme S1. Proposed catalytic cycle of the hydroarylation reaction of 5a.- 8 -Scheme S2. Hydroarylation reaction of 5c with 2bScheme S3. Hydroarylation polyaddition of 5c with 7c- 9 -NMR and MS spectraFigure S1. 1H NMR spectra of the model reaction of 1a with 2a (400 MHz, CDCl3, r.t.).Figure S2. 1H NMR spectra of the model reaction of 1b with 2a (400 MHz, CDCl3, r.t.).- 10 -Figure S3. 1H NMR spectra of the model reaction of 1c with 2a (600 MHz, CDCl3, r.t.).Figure S4. 1H NMR spectra of the model reaction of 1d with 2a (600 MHz, CDCl3, r.t.).- 11 -Figure S5. 1H NMR spectra of the model reaction of 1e with 2a (600 MHz, CDCl3, r.t.).Figure S6. 1H NMR spectra of the model reaction of 1b with 2a under the optimized conditions(Table S1 Entry 4, 400 MHz, CDCl3, r.t.).- 12 -Figure S7. 1H NMR spectra of the model reaction of 5a with 2b (600 MHz, CDCl 3, r.t.).Figure S8. 1H NMR spectrum of 6ab (600 MHz, CDCl3, r.t.).- 13 -Figure S9. 2D 1H NMR spectra of 6ab (600 MHz, CDCl3, r.t.). (a) COSY NMR. (b) NOESY NMR.Figure S10. 13C{1H} NMR spectrum of 6ab (150 MHz, CDCl3, r.t.).- 14 -Figure S11. 1H NMR spectra of the model reaction of 5b with 2b (600 MHz, CDCl 3, r.t.).Figure S12. 1H NMR spectra of the deuterium exchange experiment of 5a (600 MHz, CDCl 3, r.t.).- 15 -Figure S13. 1H NMR spectra of the deuterium exchange experiment of 5b (600 MHz, CDCl3, r.t.).Figure S14. MALDI-TOF MS of Paa- 16 -Figure S15. 1H NMR spectra of the model reaction of 5c with 2b (400 MHz, CDCl3, r.t.).Figure S16. 1H NMR spectrum of 6cb (600 MHz, CDCl3, r.t.).- 17 -Figure S17. 13C{1H} NMR spectrum of 6cb (150 MHz, CDCl3, r.t.).Figure S18. 1H NMR spectrum of Pcb; reaction time of 24 h (400 MHz, CDCl3, r.t.).- 18 -Figure S19. 1H NMR spectrum of Pcb; reaction time of 48 h (400 MHz, CDCl3, r.t.).Figure S20. MALDI-TOF MS of Pcb- 19 -Figure S21. 1H NMR spectrum of Pcc (400 MHz, C2D2Cl4, r.t.).Figure S22. MALDI-TOF MS of Pcc- 20 -Figure S23. 1H NMR spectrum of 5a (600 MHz, CDCl3, r.t.).Figure S24. 1H NMR spectrum of 5b (600 MHz, CDCl3, r.t.).- 21 -Figure S25. 1H NMR spectrum of 5c (600 MHz, CDCl3, r.t.).Figure S26. 1H NMR spectrum of 8a (600 MHz, CDCl3, r.t.).- 22 -Figure S27. 1H NMR spectrum of 8b (600 MHz, CDCl3, r.t.).GPC chartsFigure S28. GPC charts of synthesized PAVs.(a) Paa. (b) Pcb; Reaction time = 24 h. (c) Pcb; Reaction time = 48 h.- 23 -DFT calculations and X-ray crystallographic dataCrystal structure determination (Figure S30)Intensity data were collected on a Bruker SMART APEX II ULTRA with Mo Kα radiation. A full matrix least-squares refinement was used for non-hydrogen atoms with anisotropic thermal parameters using theSIR2002 or the SIR2014 program. CCDC 2334324-2334326 contain the supplementary crystallo-graphic data forthis paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailingdata_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road,Cambridge CB2 1EZ, UK; fax: +44 1223 336033.Table S2. Crystallographic data of 5a, 5b, and 5c5a 5b 5cEmpirical Formula C16H12N4 C16H12N4 C19H15N5Formula Weight 260.30 260.30 313.36Crystal Color colorless colorless colorlessCrystal Dimensions / mm 0.326 x 0.276 x 0.082 0.050 x 0.050 x 0.020 0.476 x 0.082 x 0.062Crystal System triclinic monoclinic orthorhombicLattice Parametersa / Å 3.8226 5.4302(8) 21.810(4)b / Å 10.5361 18.624(3) 4.1280(7)c / Å 15.1908 6.5107(10) 8.1510(13)β / deg. 93.0010 108.056(2) 90.0000V / Å3 605.6804 626.03(17) 733.9(2)Space Group P-1 (#2) P21/n (#14) P21212 (#18)Z 2 2 2D / gcm-3 1.427 1.381 1.418F000 272.00 272.00 328.00μ(MoKα) / cm-1 0.891 0.862 0.888Reflection/Parameter Ratio 11.52 15.27 14.64R1 (I > 2.00σ(I)) 0.0409 0.0423 0.0385R (All reflections) 0.0451 0.0600 0.0398wR2 (All reflections) 0.1272 0.1025 0.1127Goodness of Fit Indicator 1.098 1.057 1.139CCDC Number 2334326 2334325 2334324- 24 -Figure S29. Molecular geometries of 5a, 5b, and 5c optimized by DFT calculationsusing Gaussian at the B3LYP/6-31G(d) level.Figure S30. ORTEP drawing of 5a, 5b, and 5c by X-ray crystallographic analyses.- 25 -Optical and electronic dataTable S3. Optical properties of monomer, model compounds, and PAVsCompoundCHCl3 solution [a] Film state [b]λabs (nm) λem (nm) PLQY [c] (%) λabs (nm) λem (nm) PLQY [c] (%)5a 267, 308 358 - - - -6ab 302, 361 425 84 298, 363 459 138a 365 418 87 - [d] - [d] - [d]Paa 405 460 80 406 472 206cb 283, 375 449 71 282, 373 482 6.58b 377 419 79 377 447 5.9Pcb 406 454 66 408 475 6.0[a] Concentration of 5.0 x 10-6 M. [b] Spin-coated film. [c] Photoluminescence quantum yield. [d] Spin-coated filmwas not able to fabricate because the solubility of 8a was quite low.Figure S31. Optical spectra of Paa and Pcb in CHCl3 solutions (5.0 x 10-6 M)(a) UV-vis absorption spectra. (b) PL spectra.Figure S32. Comparison of optical spectra of the naphthalene- and carbazole-based model compoundsin CHCl3 solutions (5.0 x 10-6 M). (a) UV-vis absorption spectra. (b) PL spectra.- 26 -Figure S33. Optical spectra of naphthalene derivatives in the film states.(a) UV-vis absorption spectra. (b) PL spectra.Figure S34. Optical spectra of carbazole derivatives in the film states.(a) UV-vis absorption spectra. (b) PL spectra.Figure S35. AFM images (5 x 5 µm) of spin-coated films- 27 -OLED properties of PaaFigure S36. CIE chromaticity diagram from the EL spectrum of Paa.Figure S37. EQE vs current density plots for the fabricated OLED of Paa.Configuration ITO/PEDOT:PSS (40 nm)/Paa (47 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm).References[1] R. Iwamori, R. Sato, J. Kuwabara, T. Yasuda, T. Kanbara, Macromol. Rapid Commun. 2021, 42, 2100283.[2] A. Correa, C. Bolm, Adv. Synth. Catal. 2007, 349, 2673-2676.[3] Z. Liu, D. Cao, Y. Chen, Q. Fang, Dyes Pigments 2010, 86, 63-67.