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

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[Synthesis of Bithiazole‐Based Poly(arylenevinylene)s via Co‐Catalyzed Hydroarylation Polyaddition and Tuning of Their Optical Properties by <i>N</i>‐Methylation and <i>N</i>‐Oxidation](https://mdr.nims.go.jp/datasets/36554b10-5f3e-4246-b1c2-2f22226479b9)

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Synthesis of Bithiazole‐Based Poly(arylenevinylene)s via Co‐Catalyzed Hydroarylation Polyaddition and Tuning of Their Optical Properties by N‐Methylation and N‐OxidationRESEARCH ARTICLEwww.mrc-journal.deSynthesis of Bithiazole-Based Poly(arylenevinylene)s viaCo-Catalyzed Hydroarylation Polyaddition and Tuning ofTheir Optical Properties by N-Methylation and N-OxidationBoya Li, Ryota Iwamori, Junpei Kuwabara, Takeshi Yasuda, and Takaki Kanbara*Bithiazole-based poly(arylenevinylene) is synthesized via the Co-catalyzedhydroarylation polyaddition of N,N,N′,N′-tetrahexyl-(2,2′-bithiazole)-4,4′-dicarboxamide with 2,7-diethynyl-9,9-bis(2-ethylhexyl)fluorene in aregioselective manner. The introduction of the 2,2′-bithiazole unit deepens thehighest occupied molecular orbital (HOMO) and lowest unoccupiedmolecular orbital (LUMO) energy levels of the polymer compared to theanalogous bithiophene-based poly(arylenevinylene). N-Methylation andN-oxidation of the thiazole moiety further deepen the HOMO and LUMOenergy levels of the polymer, which is attributed to the enhancedelectron-withdrawing effect. The N-oxidized polymer exhibits a highphotoluminescence quantum yield and serves as an emitting material in anorganic light-emitting diode, and its deep HOMO energy level efficientlyrestrains the trapping of holes in the host poly(vinylcarbazole) matrix.B. Li, R. Iwamori, J. Kuwabara, T. KanbaraInstitute of Pure and Applied SciencesUniversity of Tsukuba1-1-1 Tennodai, Tsukuba, Ibaraki 305–8573, JapanE-mail: kanbara@ims.tsukuba.ac.jpJ. KuwabaraTsukubaResearchCenter for EnergyMaterials Science (TREMS)Institute of Pure andAppliedSciencesUniversity of Tsukuba1-1-1 Tennodai, Tsukuba, Ibaraki 305–8573, JapanT. YasudaResearchCenter forMacromolecules andBiomaterialsNational Institute forMaterials Science (NIMS)1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, JapanThe ORCID identification number(s) for the author(s) of this articlecan be found under https://doi.org/10.1002/marc.202401082[The copyright line for this article was changed on 12 February 2025 afteroriginal online publication.]© 2025 The Author(s). Macromolecular Rapid Communicationspublished by Wiley-VCH GmbH. This is an open access article under theterms of the Creative Commons Attribution-NonCommercial-NoDerivsLicense, which permits use and distribution in any medium, provided theoriginal work is properly cited, the use is non-commercial and nomodifications or adaptations are made.DOI: 10.1002/marc.2024010821. IntroductionPoly(arylenevinylene)s (PAVs) are an at-tractive family of 𝜋-conjugated polymers.Owing to their high planarity, they havebeen extensively applied as organic opto-electronic materials, particularly organiclight-emitting diodes (OLEDs) and or-ganic photovoltaics (OPVs).[1–6] Thesepolymers can be synthesized using sev-eral methods.[7,8] A recent promisingsynthetic approach is polyaddition viahydroarylation of arenes with aromaticdiynes, which eliminates the production ofbyproducts from the monomers.[9–15] Wepreviously demonstrated the Cp*Co(III)-catalyzed hydroarylation polyaddition ofN,N,N′,N′-tetrahexyl-(2,2′-bithiophene)-4,4′-dicarboxamide with aromatic diynes(Figure 1a).[12,15] The amide directinggroups facilitated site- and regioselectivepolyaddition, and the synthesized PAVs served as emitting mate-rials in OLEDs and p-type semiconducting materials in OPVs.Thiazole is a well-known thiophene analog, which is moreelectron-deficient than thiophene. Displacement of a bithio-phene unit with a bithiazole unit in the 𝜋-conjugated polymerstructure deepens both the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital (LUMO)energy levels.[16–20] Owing to intermolecular S···S and S···N in-teractions, bithiazole-based conjugated polymers tend to exhibitplanar structures.[21] In addition, N-methylation of the thiazolemoiety creates a positive charge on the nitrogen atom, deep-ening both the HOMO and LUMO energy levels and having amore pronounced effect on the LUMO energy levels. Thus, a nar-rower bandgap and red-shifted absorption were observed for N-methylated bithiazole-based conjugated polymers.[22,23] A similarsynthetic strategy was demonstrated by introducing an N-oxidegroup into bithiazole-based conjugated polymers.[24,25] Fromthese observations, we herein designed N,N,N′,N′-tetrahexyl-(2,2′-bithiazole)-4,4′-dicarboxamide (1a) as a new targeting aro-matic monomer for hydroarylation polyaddition (Figure 1b), giv-ing new bithiazole-based PAVs. We anticipated that the introduc-tion of the 2,2′-bithiazole unit would deepen the HOMO andLUMO energy levels of PAVs compared to the bithiophene-basedanalogs. In addition, N-methylation and N-oxidation of the thia-zole moiety led to the generation of electron-deficient polymerbackbones (Figure 1c). The N-oxidized PAV has a high photo-Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (1 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbHhttp://www.mrc-journal.demailto:kanbara@ims.tsukuba.ac.jphttps://doi.org/10.1002/marc.202401082http://creativecommons.org/licenses/by-nc-nd/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fmarc.202401082&domain=pdf&date_stamp=2025-02-07www.advancedsciencenews.com www.mrc-journal.deFigure 1. Co-catalyzed hydroarylation polyaddition and polymer reactions.luminescence property as well as a deep HOMO energy level,which contributes to its electroluminescence property as a guest-emitting material for OLEDs.2. Results and Discussion2.1. Model ReactionTo assess the reactivity of 1a, we conducted a small molecularmodel reaction, as described in our previous study.[12] The hy-droarylation of 1a with 4-ethynyltoluene (2a) was performed indry 1,2-dichloroethane (DCE, 0.05 M) at 30 °C in the presence of[Cp*Co(CH3CN)3](SbF6)2 (2 mol%) and neodecanoic acid (NDA,30mol%) (Scheme 1). The conversion of 1a to dialkenylated prod-uct (3aa) was confirmed by time-course analyses using nuclearmagnetic resonance (NMR) spectroscopy. The NMR yield of 3aareached 60% after 1 h, and quantitative consumption of 1a wasachieved after 24 h (Figure S1, Supporting Information). The re-activity of 1a was slightly lower than that of its analogous bithio-phenemonomer. The presence of electron-withdrawing nitrogenatoms weakened the ability of the carbonyl oxygen in the amidegroups to coordinate with the Co catalyst. This feature lowersthe reactivity of the concerted metalation-deprotonation (CMD)step, which is the rate-determining step in the catalytic cycle ofhydroarylation (Scheme S1, Supporting Information). Neverthe-less, the hydroarylation reaction proceeded selectively at the 5,5′-positions of 1a; 3aa was isolated as the E,E-isomer in 81% yield(Figure S2, Supporting Information). These results indicate that1a applies to hydroarylation polyadditions with a longer reactiontime than the analogous bithiophene monomer.2.2. Polyaddition ReactionSubsequently, the hydroarylation polyaddition of 1a with 2,7-diethynyl-9,9-bis(2-ethylhexyl)fluorene (4a) was performed underthe same reaction conditions as the small molecular model reac-tion (Scheme 2). The reaction was quenched after 4 h, as the reac-tion mixture became viscous. The corresponding PAV (Paa) wasobtained in 91% yield with a number-average molecular weight(Mn) of 40000 and a polydispersity index (Mw/Mn) of 2.8, whichScheme 1. Small molecular model reaction of 1a with 2a.Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (2 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2025, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202401082 by National Institute For, Wiley Online Library on [07/05/2025]. 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 Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deScheme 2. Hydroarylation polyaddition of 1a with 4a.were estimated by gel permeation chromatography (GPC). Whenthe reaction temperature was raised to 70 °C, the polyaddition re-action gave Paa in 92% yield, with anMn of 77000 andMw/Mn of3.0 (Figure S13a, Supporting Information). All signals in the 1HNMR spectrum of Paa were assigned to the repeating structurewith a 1,2-vinylene unit and to each terminal structure (Figure 2);there was no minor signal derived from the 1,1-vinylidene unit(5.5–5.0 ppm). To check themonomer scope of the reactions with1a, we also conducted the hydroarylation polyaddition of 1a with2,7-bis(4-ethynylphenyl)-9,9-di(n-octyl)fluorene (4b) (Scheme S2,Figure S3, Supporting Information). The reactivity of the diynemonomer was increased by introducing a phenylene spacer be-tween the alkyne and fluorene moieties, resulting in a high yieldand molecular weight within a reaction time of only 10 min(Figure S13b, Supporting Information). Paa and Pab were alsosynthesized at different temperatures and reaction times, yield-ing the corresponding PAVs with reasonable molecular weightsin good yields (Table S1, Supporting Information).2.3. Polymer ReactionsMethyl trifluoromethanesulfonate (MeOTf), a strong methylat-ing reagent, is commonly used for N-methylation of thiazolederivatives.[22,23] Therefore, we selected MeOTf to perform theN-methylation of Paa (Mn = 77 000). According to a previousreport,[22] the reaction was carried out for 7 d in dry chloroformat 50 °C using 7 equiv. of MeOTf (Table 1, Entry 2, and SchemeFigure 2. 1H NMR spectrum of Paa (Mn = 77000, 600 MHz, C2D2Cl4,373 K).S3, Supporting Information). The N-methylated product Paa-Mwas purified and obtained in 65% yield, calculated based on theN-methylation ratio. From the 1H NMR analysis of Paa-M, thesignal derived fromN─CH3 of methylated thiazole unit was con-firmed at 𝛿 4.54 ppm. The N-methylation ratio was calculatedfrom the integral ratio of the signals of aromatic C─H bonds(10H at 𝛿 8.2–7.2 ppm) to those of N─CH3 (maximum value =6H), resulting in 37%modification (Figure S4, Supporting Infor-mation for the detail of calculation method). The N-methylationratio was also calculated from the 𝛼-methylene protons of thealkyl amides (8H at 𝛿 4.0–3.2 ppm) to N─CH3; the value wasthe same as that from aromatic C─H bonds. Further structuralanalysis was conducted using Fourier transform infrared (FT–IR) spectroscopy. The FT–IR spectrum showed strong infraredvibration bands of triflate ions at 1262, 1160, 1033, and 638 cm−1(Figure S11, Supporting Information).[22,23] Paa-M with differentmethylation ratios were obtained by changing the reaction tem-perature and feeding amount of MeOTf (Table 1 and Figures S5–S7, Supporting Information). Increasing the amount of MeOTfinitially increased the methylation ratio (Entries 1 and 2); how-ever, excess MeOTf decreased the methylation ratio (Entry 3).Higher reaction temperatures also increased the methylation ra-tio (Entry 4). Due to the steric hindrance caused by the amideside chains of the bithiazole backbone, introducing N─CH3 atboth sites is considered challenging, exceeding 50% of the N-methylation ratio is difficult.Subsequently, the N-oxidation reaction of Paa (Mn = 77 000)was performed. Based on the literature,[24] the reaction wasconducted using 6 equiv. of meta-chloroperoxybenzoic acid (m-CPBA) in dry DCE at 30 °C for 96 h (Scheme S4, Support-ing Information). Insoluble solids precipitated from the reac-tion mixture. The N-oxidation product Paa-O was purified andobtained in 56% yield, which was calculated based on the N-Table 1. Results of N-methylation reaction of Paa.Entrya) PAVs MeOTf equiv. Temp./°C Yieldb) /% N-methylation ratioc) /%1 Paa-M-11 3.5 50 69 112 Paa-M-37 7 50 65 373 Paa-M-27 14 50 62 274 Paa-M-50 7 70 66 50a)Paa (Mn = 77 000, 0.02 mmol) was reacted with MeOTf (prescribed equivalent)in CHCl3 (0.01 m) at the prescribed temperature for 7 d;b)The yields were calcu-lated based on theN-methylation ratio;c)Calculated from the 1HNMR spectra usingacetone-d6 at room temperature.Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (3 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2025, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202401082 by National Institute For, Wiley Online Library on [07/05/2025]. 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 Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deFigure 3. Chemical structures of PAVs.oxidation ratio. Because Paa-O showed high solubility only inTHF, the 1H NMR spectrum of Paa-O was measured using asolvent mixture of THF:CDCl3 = 1:1. From the 1H NMR anal-ysis of Paa-O, the signal derived from the 𝛼-methylene protonsof dialkyl amides was confirmed at 𝛿 5.8–4.8 ppm. These signalsexhibit significant downfield shifts, which are attributed to theelectron-withdrawing effect of N-oxidation. The N-oxidation ra-tio was calculated from the integral ratio of the vinylene struc-ture (2H at 𝛿 7.0–6.7 ppm) to that of the 𝛼-methylene protons ofdialkyl amides (maximum value = 8H), resulting in 57% mod-ification (Figure S8, Supporting Information for details of thecalculation method). Further structural analysis was conductedusing FT–IR spectroscopy, which showed strong infrared vibra-tion bands of the N─O bond at 1163 cm−1 (Figure S12, Support-ing Information).[26,27]2.4. Optical PropertiesThe optical properties of the synthesized PAVs were investigated.The structures of the PAVs subjected to optical properties areshown in Figure 3. First, we discuss the optical spectra of thePAVs in dilute solutions (Figure 4 and Table S2, SupportingInformation). In CHCl3 solution, the ultraviolet-visible (UV–vis)absorption and photoluminescence (PL) spectra of Paa exhibitedredshifts compared to the analogous bithiophene polymer P0,attributed to the rigid and planar structure of the bithiazolebackbone (Figure S14, Supporting Information). A similar trendwas observed for Pab compared to P1 (Figure S15, SupportingInformation). As theN-methylation ratio of Paa-M increased, theabsorption intensity of the original Paa decreased, and a long-wavelength absorption band (550–600 nm) emerged (Figure 4a).This result is similar to those reported in the literature.[22,23] Inour experiment, even a small amount of N-methylation can sig-nificantly affect the overall 𝜋-conjugated system of the polymer,leading to disproportionate changes in the absorption bands. ThePL spectra of Paa-M also red-shifted compared with those of Paa(Figure S16, Supporting Information). The photoluminescencequantum yield (PLQY) of Paa-M was lower than that of Paa butgradually increased with the degree of N-methylation (TableS2, Supporting Information). The UV–vis absorption spectrumof Paa-O in THF showed a blue shift compared to that of Paa(Figure 4b). The N-oxidized bithiazole-based conjugated poly-mers typically exhibit redshifts in absorption compared with theoriginal polymers.[24,25] However, alternation of the side chainsof the N-oxidized polymers from alkyl to amide groups resultedin blue-shifted absorption, which was considered to limit theeffective conjugation length.[27] Paa-O exhibited a similar 𝜆emto Paa and maintained a high PLQY (Figure S17, SupportingInformation).The optical properties of the PAVs in the film state werecompared with those in a dilute solution (Table 2, Figure 5a). ForFigure 4. UV–vis absorption spectra of a) Paa and Paa-M in the CHCl3 solution (5.0 × 10−6 m) and b) Paa and Paa-O in the THF solution (5.0 × 10−6 m).Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (4 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2025, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202401082 by National Institute For, Wiley Online Library on [07/05/2025]. 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 Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deTable 2. The optical properties of PAVs in the film states.PAVs 𝜆max /nm 𝜆edge /nm Egopt a)/eV EHOMOb)/eV ELUMOc)/eV PLQY d)/%P0 490 549 2.26 −5.31 −2.71 10.7Paa 530 553 2.24 −5.52 −2.99 13.6Paa-O 452 540 2.30 −5.77 −3.15 23.7Paa-M-27 529 624 1.99 −5.80 −3.63 7.4Paa-M-50 556 626 1.98 −5.80 −3.64 7.6a)Optical bandgap from the absorption edge;b)EHOMO was determined by UPS;c)ELUMO was determined by LEIPS;d)Photoluminescence quantum yield.Paa-M, no notable shifts were observed in either the absorptionor the PL spectra between the film and solution states (FigureS18, Supporting Information). In contrast, Paa and Paa-O exhib-ited significant redshifts in their PL spectra, by 56 and 60 nm,respectively, while no significant shifts in 𝜆max were observedin their absorption spectra between the film and solution states(Figure S18, Supporting Information). The PLQY of all the PAVsdecreased in the film state compared to that in the solutionstate because of aggregation-caused quenching (ACQ),[13,28,29]whereas Paa-O film retained a relatively high PLQY of 23.7%.The optical bandgap (Egopt) of each PAV in the film state wascalculated using the absorption edge. N-methylation narrowedthe Egopt by 0.3 eV compared to the original Paa, while Paa-Oexhibited a wider Egopt than Paa.The HOMO and LUMO energy levels (EHOMO and ELUMO)of the PAVs in the thin films were measured using ultravio-let photoelectron spectroscopy (UPS) and low-energy inversephotoelectron spectroscopy (LEIPS),[30] respectively (Table 2,Figures 5b and S19–S25, Supporting Information). Comparedwith bithiophene-based PAV (P0),[12] the frontier orbital energylevels of bithiazole-based Paa became deeper by 0.2 eV owing tothe electron-withdrawing effect of bithiazole moiety. The rela-tionship between the energy levels of P1 and Pab was consistentwith that between P0 and Paa (Figure S26, Supporting Informa-tion). TheN-methylation of Paa effectively deepened both EHOMOand ELUMO, especially the ELUMO by 0.6 eV. As the LUMO of Paamainly resided at the nitrogen atoms on the bithiazole moiety,[22]the ELUMO of Paa-Mwas further deepened compared to that of theEHOMO owing to the electron-withdrawing effect, even with a lowN-methylation ratio. The frontier orbital energy levels of Paa-M-27 were approximately the same as those of Paa-M-50. Althoughthe 𝜆max of Paa-M red-shifted with increasing N-methylationratio, the Egopt, EHOMO, and ELUMO of Paa-M remained constantowing to the unchanged absorption edge. The N-oxidation ofPaa also deepened both EHOMO and ELUMO. However, the ELUMOof Paa-O was shallower than that of Paa-M by 0.5 eV.2.5. OLED PropertiesBecause the Paa-O film exhibited a high PLQY in both the dilutesolution and film states, the electroluminescent (EL) propertiesof the OLED were evaluated. Poly(vinylcarbazole) (PVK) with 2.9wt% Paa-O in THF was spin-coated to form a hole-transport PVKfilm doped with Paa-O (see Supporting Information for detailsof OLED fabrication). Because of the large overlap between thePL spectrum of the PVK thin film and the absorption spectrumof the Paa-O solution (Figure S27, Supporting Information), theexciton energy of PVK is expected to be transferred to Paa-Ovia Förster resonance energy transfer.[31–35] Efficient emissionscan be obtained from excited Paa-O by doping a small amountof Paa-O into a PVK thin film. The EL spectrum in Figure 6was representative of ≈10 cd m−2, and the coordinates of theCIE chromaticity diagram were x = 0.437 and y = 0.528 (FigureS28, Supporting Information). The current efficiency reached6.42 cd A−1 at a current density of 0.412 mA cm−2, and themaximum external quantum efficiency (EQE) of the OLEDwas 2.10% (Figure S29, Supporting Information). The EQE ofFigure 5. a) UV–vis absorption spectra of Paa, Paa-M, and Paa-O in film states. b) Energy level diagram of PAVs.Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (5 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2025, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202401082 by National Institute For, Wiley Online Library on [07/05/2025]. 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 Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deFigure 6. PL and EL spectra of Paa-O.the OLED with the same structure, where Paa-O was replacedwith Paa, was 1.39%. The EL spectrum was similar to the PLspectrum of Paa-O in dilute solution, whereas no emissionpeaks corresponding to PVK and Paa-O in the film states wereobserved (Figure 6). As expected, this behavior shows that Paa-Odispersed in the PVK layer was efficiently excited by the Försterresonance energy transfer of the exciton energy of PVK. Therelationship between the HOMO energy levels of the dopant andhost matrix is generally important for the hole mobilities of thehost matrix.[36,37] In our experiments, the HOMO energy level ofPaa-O was nearly the same as that of PVK (−5.76 eV); therefore,it appears that Paa-O does not act as a hole trap in the PVK layer,i.e., doping a small amount of Paa-O into PVK does not reducethe hole mobility of PVK (Figure S30, Supporting Information).3. ConclusionIn summary, bithiazole-based poly(arylenevinylene)s were syn-thesized via Co-catalyzed hydroarylation polyaddition, followedbyN-methylation andN-oxidation via polymer reactions. The op-tical spectra of the synthesized bithiazole-based PAVs were red-shifted compared with those of their bithiophene-based analogs.N-Methylation of bithiazole-based Paa resulted in further red-shifted absorption and narrow bandgaps, whereas N-oxidationof Paa induced blue-shifted absorption. The HOMO and LUMOenergy levels of the bithiazole-based PAVs were deeper thanthose of the corresponding bithiophene-based analogs, owing tothe electron-withdrawing properties of the bithiazole units. N-Methylation further deepened the LUMO energy level, whereasN-oxidation deepened the LUMO and HOMO energy levels.Therefore, the N-modification serves as a promising tool for tun-ing a wide range of PAV optical properties and energy levels. No-tably, Paa-O exhibited a high PLQY and a deep HOMO energylevel, highlighting its potential as a guest-emitting material forOLEDs.4. Experimental SectionSynthesis of Paa: To a stirred solution of 1a (177.28 mg, 0.30 mmol)and 4a (131.61 mg, 0.30 mmol) in anhydrous DCE (6.0 mL) were added[Cp*Co(CH3CN)3](SbF6)2 (4.73 mg, 0.0060 mmol) and NDA (17.0 μL,0.090 mmol). The reaction mixture was stirred for 4 h at 70 °C under anitrogen atmosphere. Then, the reaction mixture was diluted with CHCl3(50 mL) and poured into an NH3 solution (28% in water, 50 mL). The or-ganic layer was washed with NH3 solution and distilled water (100 mL ×2). The organic layer was dried over sodium sulfate and filtered througha Celite plug. The solution of CHCl3 was concentrated and reprecipitatedinto methanol. The precipitate was collected by filtration and dried undera vacuum. A polymeric product (Paa) was obtained as an orange solid in92% yield (283.4 mg, Mn = 77000, Mw/Mn = 3.0). 1H NMR (600 MHz,C2D2Cl4, 373 K): 𝛿 = 7.74 (d, J = 9.8, 2H), 7.54 (m, 6H), 7.19 (d, J = 15.1,2H), 3.55 (br s, 8H), 2.12 (br s, 4H), 1.80 (br s, 8H), 1.39 (br s, 24H),0.27–1.15 (m, 42H). Anal. calcd. for C65H96N4O2S2: C 75.82, H 9.40, N5.44; found: C 74.70, H 9.73, N 5.42.Pab was obtained by the same procedure. (Supporting Information)Synthesis of Paa-M-37: A solution of Paa (20.59mg, 0.020mmol basedon the repeating unit) and MeOTf (15.8 μL, 0.14 mmol) in anhydrousCHCl3 (2.0 mL) was stirred for 7 days at 50 °C under a nitrogen atmo-sphere. During the reaction, the color of the solution gradually changedfrom orange to red and ultimately to purple. The reaction product was con-centrated and reprecipitated into hexane. The precipitate was washed withwater and dried under a vacuum. An N-methylated product (Paa-M-37)was obtained as a purple solid in 65% yield. (calculated based on the N-methylation ratio, 15 mg) 1H NMR (600 MHz, Acetone-d6, r.t.): 𝛿 = 7.22–8.18 (m, 10H, aromatic C─H bonds), 4.36–4.69 (s, 2.22H,N─CH3), 3.17–3.86 (m, 8H, 𝛼-methylene protons of alkyl amides). 2.15 (br s, 8H), 1.61–1.98 (m, 8H), 1.10–1.58 (m, 24H), 0.37–1.08 (m, 42H). TheN-methylationratio = 37%Paa-M-11, Paa-M-27, and Paa-M-50 were obtained by the same proce-dure. (Supporting Information)Synthesis of Paa-O: A solution of Paa (61.78mg, 0.060mmol based onthe repeating unit) andm-CPBA (62.13 mg, 0.36 mmol) in anhydrous DCE(3.0mL) was stirred for 96 h at 30 °C under a nitrogen atmosphere. Duringthe reaction, insoluble solids in DCE were observed precipitating from thereaction mixture. After removing DCE, the precipitate was washed threetimes with hexane and dried under vacuum. An N-oxidized product (Paa-O) was obtained as an orange solid in 56% yield. (calculated based on theN-oxidation ratio, 35.4 mg) 1H NMR (600 MHz, THF: CDCl3 = 1:1, r.t.): 𝛿= 7.04–7.63 (m, 8H), 6.75–7.00 (m, 2H, the vinylene structure), 4.86–5.79(m, 4.56H, the 𝛼-methylene protons of alkyl amides afterN-oxidation). TheN-oxidation ratio = 57%Supporting InformationSupporting Information is available from the Wiley Online Library or fromthe author.AcknowledgementsThe authors thank the Chemical Analysis Division and theOPENFACILITY,Research Facility Center for Science and Technology, University of Tsukuba,for the measurements of NMR, APCI-MS, LEIPS, and UPS. The LEIPS andUPSmeasurements were supported by “Advanced Research Infrastructurefor Materials and Nanotechnology in Japan (ARIM)” of the Ministry of Ed-ucation, Culture, Sports, Science, and Technology (MEXT); proposal num-ber JPMXP1224BA0038. The authors are grateful to Dr. Ayako Okano forfruitful discussions about the LEIPS and UPS measurements. This workwas partly supported by JSPS KAKENHI Grant Numbers 23K04835 and23KJ0240.Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are available from the cor-responding author upon reasonable request.Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (6 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2025, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202401082 by National Institute For, Wiley Online Library on [07/05/2025]. 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Cameron, W. J. Peveler, H. A.Yu, P. J. Skabara, Synth. Met. 2020, 268, 116504.Macromol. Rapid Commun. 2025, 46, 2401082 2401082 (7 of 7) © 2025 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2025, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202401082 by National Institute For, Wiley Online Library on [07/05/2025]. 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 Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.de Synthesis of Bithiazole-Based Poly(arylenevinylene)s via Co-Catalyzed Hydroarylation Polyaddition and Tuning of Their Optical Properties by N-Methylation and N-Oxidation 1. Introduction 2. Results and Discussion 2.1. Model Reaction 2.2. Polyaddition Reaction 2.3. Polymer Reactions 2.4. Optical Properties 2.5. OLED Properties 3. Conclusion 4. Experimental Section Supporting Information Acknowledgements Conflict of Interest Data Availability Statement Keywords