# Fileset

[Iwamori_MARC24.pdf](https://mdr.nims.go.jp/filesets/e7b98888-5479-4aee-b067-a1de133f45e4/download)

## Creator

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

## Rights

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/)

## Other metadata

[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)

## Fulltext

Microsoft Word - Iwamori_MARC24COMMUNICATION1Molecular Design of Naphthalene- and Carbazole-BasedMonomers for Regiospecific Synthesis of Poly(arylenevinylene)svia Co-catalyzed Hydroarylation PolyadditionRyota Iwamori,[a] Junpei Kuwabara,[a,b] Takeshi Yasuda,[c] Takaki Kanbara*[a][a] R. Iwamori, Prof. J. Kuwabara, Prof. T. KanbaraInstitute of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8573, Japan.E-mail: kanbara@ims.tsukuba.ac.jp[b] Prof. J. KuwabaraTsukuba 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.[c] Dr. T. YasudaResearch Center for Macromolecules and Biomaterials, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.Abstract: This study focuses on the development of regiospecifichydroarylation polyaddition of naphthalene- and carbazole-basedmonomers with diynes under mild reaction conditions at roomtemperature. A 1-pyrazole substituent serves as an appropriatedirecting group for a Co-catalyst to efficiently activate the C–H bondsof generally inactive six-membered aromatic hydrocarbons. The 1-pyrazole groups in 2,6-di(1-pyrazolyl)naphthalene adopt planarconformations and act as directing groups, resulting in a smoothhydroarylation reaction. In contrast, the reaction with 1,5-di(1-pyrazolyl)naphthalene did not proceed. The polyaddition reaction of2,6-di(1-pyrazolyl)naphthalene selectively proceeded at 3,7-positionsunder mild reaction conditions at 30 °C, and yielded correspondingpoly(arylenevinylene) with high molecular weight. This moleculardesign is also applicable to the hydroarylation polyaddition ofcarbazole; the polyaddition reaction of 9-(2-ethylhexyl)-3,6-di(1-pyrazolyl)carbazole selectively occurred at 2,7-positions. The opticaland electronic properties of the synthesized compounds wereevaluated. The obtained poly(arylenevinylene)s served as anemitting material in organic light-emitting diode. This study aims todevelop a Co-catalyzed hydroarylation polyaddition via C–Hactivation of generally inactive polyaromatic hydrocarbons undermild conditions.Transition-metal-catalyzed C–H functionalization is a powerfulapproach for C–C bond formation between aromatic compoundswithout prior preparation of starting materials. [1–5] This approachprovides the straightforward synthesis of a vast number ofcompounds, ranging from small biologically active molecules tomacromolecular organic materials. [1,3,6,7] In the research field ofpolymer chemistry, direct arylation polycondensation, [8–11] cross-dehydrogenative-coupling polycondensation, [9,12–16] and directalkenylation polycondensation [17–19] have been reported for thesynthesis of π-conjugated polymers via C–H activation reactions.  Poly(arylenevinylene)s (PAVs) are promising semiconductingmaterials used in organic optoelectronic devices such as organicphotovoltaics (OPVs), organic field-effect transistors (OFETs),and organic light-emitting diodes (OLEDs). [20–22] PAVs havegenerally been prepared by polycondensation [23] based on theGilch reaction,[24,25] Wittig reaction, [26–28] olefin metathesis,[29–32]Migita-Kosugi-Stille cross-coupling, [33] Mizoroki-Heck reaction,[34–36] and transition-metal-mediated dehalogenatingpolyolefination. [37–39] In recent years, hydroarylation polyadditionof alkynes has been developed to synthesize as an ideal methodfor the synthesis of PAVs because the production of by-productsfrom monomers can be eliminated. [40–43] We recently reportedthe Cp*Co(III)-catalyzed hydroarylation polyaddition of aromaticdiynes to pyrrole and thiophene derivatives for the preparation ofPAVs (Scheme 1a). [41–43] The introduction of appropriatedirecting groups promoted site- and regio-selective synthesis ofthe corresponding PAVs under mild reaction conditions even at30 °C. However, to the best of our knowledge, the C–C bondformation reaction via site-selective C–H bond activation ofpolyaromatic hydrocarbons (PAHs) at room temperature has notbeen achieved because the C–H bonds of PAHs are lessreactive than those of pyrrole and thiophene. [16,44–46] Thecleavage of C–H bonds in PAHs generally requires harshreaction conditions because of their high activation energies.To overcome this limitation, we explored the appropriatemonomer structures and reaction conditions for the site- andregio-selective hydroarylation polyaddition of PAHs using a Co-catalyst. As poly(naphthalene) and poly(naphthalenevinylene)derivatives linked at β-positions show high fluorescence quantum yields (Φfl > 0.7) and have been applied to OLEDs, [47,48]2,6-di(1-pyrazolyl)naphthalene was designed as a newnaphthalene monomer. A site- and regio-selective hydroarylationpolyaddition proceeded smoothly under mild reaction conditionsto obtain the corresponding PAV (Scheme 1b). In addition, thismonomer design was applicable to the hydroarylationpolyaddition of a carbazole unit. Furthermore, the optical andelectronic properties of the synthesized PAVs were evaluated.Scheme 1. Cp*Co(III)-catalyzed hydroarylation polyaddition.COMMUNICATION2In the Cp*Co(III)-catalyzed hydroarylation reaction, thestructure of the directing group is a crucial factor that affects thereactivity of the C–H activation step. [49–51] Therefore, to find anappropriate directing group for the Co-catalyzed hydroarylationof less reactive six-membered aromatic compounds, small-molecular model reactions of mono-substituted benzenes (1)with 4-ethynyltoluene (2a) were tested. Commonly usedpyridine-type nitrogens and carbonyl-type oxygens wereexplored to improve the conversion of benzenes to alkenylatedproducts (Figure 1, and Figures S1–S5). We first attempted themodel reaction of 2-phenylpyridine (1a) with 2.1 equivalent of 2ain the presence of [Cp*Co(CH3CN)3](SbF6)2 (5 mol%) andneodecanoic acid (NDA, 60 mol%) in tetrahydrofuran (THF, 0.1M) at 30 °C for 24 h under N2 atmosphere. The product yields ofthe reaction mixtures were calculated from the nuclear magneticresonance (NMR) spectra. The reaction afforded the mono-alkenylated product (3aa) in 30% yield (Figure S1). Theconversion of benzene to alkenylated products improved in themodel reaction of 1-phenylpyrazole (1b) with 2a. The NMRyields of the mono-alkenylated product (3ba) and di-alkenylatedproduct (4ba) were 62% and 18%, respectively (Figure S2). Incontrast, carbonyl-type directing groups did not work underthese reaction conditions (Figures S3–S5). As a result, the 1-pyrazole substituent was found to be the appropriate directinggroup for the Co-catalyzed hydroarylation of the benzene moiety.The reaction conditions for 1b with 2a were subsequentlyoptimized for efficient hydroarylation (Table S1, Figure S6). Alow concentration of the substrate (0.05 M) and the addition ofneodecanoic acid (1 equiv.) effectively improved the conversionof 1b to 3ba and 4ba.Figure 1. Exploration of the directing group for the benzene moiety. Yields of 3and 4 were calculated by1H NMR analyses using 1,3,5-trimethoxybenzene asan internal standard (Figures S1-S5).Subsequently, 2,6-di(1-pyrazolyl)naphthalene (5a) and 1,5-di(1-pyrazolyl)naphthalene (5b) were designed for site-selectivehydroarylation reaction of naphthalene at β-positions. Small-molecular model reactions of 5a and 5b with 4-tert-butylphenylacetylene (2b) were attempted under the optimizedconditions (Scheme 2). The hydroarylation of 5a selectivelyproceeded at the 3,7-positions of the naphthalene moiety evenat 30 °C, and the dialkenylated product (6ab) was isolated in82% yield (Scheme 2a, Figures S7–S10). In contrast, thehydroarylation of 5b did not afford the correspondingdialkenylated compound (Scheme 2b, Figure S11). To elucidatethe mechanism of the site selectivity and reactivity of 5a and 5b,deuterium exchange experiments were performed in thepresence of CD3COOD instead of 2b and NDA. The selectivedeuteration of 5a was observed at the less-hindered 3,7-positions (32% D at the 3,7-positions vs. 0% D at the 1,5-positions; Scheme 3a and Figure S12). Because the Cp*Co(III)catalyst avoids steric repulsion between the Cp* ligand and theC–H bonds at 4,8-positions, [52] the excellent site-selectivity wasexhibited at the 3,7-positions (Scheme S1). In contrast,deuterium exchange in 5b rarely occurred at any position (<5%D, Scheme 3b, and Figure S13). These results indicate that the1-pyrazole groups introduced at 2,6-positions of naphthalene aresuitable for Co-catalyzed hydroarylation. In addition, themolecular geometries were optimized via density functionaltheory (DFT) calculations using Gaussian at the B3LYP/6-31G(d) level (Figures 2 and S29). Although the 1-pyrazole groupof 5a adopts planar conformations, that of 5b has difficultyforming planar conformations because of the steric hindrance ofthe C–H bond at the peri-position. The crystal structures of 5aand 5b were ascertained by X-ray crystallography (Table S2 andFigure S30). The dihedral angles between the naphthalenecores and the 1-pyrazole groups in 5a and 5b, respectively,were almost consistent with the structures optimized by DFTcalculations. These results indicate that the 1-pyrazole group,which easily adopts a planar conformation, acts as an effectivedirecting group for six-membered aromatic hydrocarbons.Scheme 2. Hydroarylation reactions of the naphthalene monomers with 2b.Scheme 3. Deuterium exchange experiments of the naphthalene monomers.COMMUNICATION3Figure 2. Rotation energies of the 1-pyrazole group of 5a and 5b. DFTcalculations were carried out at B3LYP/6-31G(d) level.Scheme 4. Hydroarylation polyaddition of the (a) naphthalene- and (b) carbazole-based monomers with diyne monomers.The hydroarylation polyaddition of 5a with 2,7-bis(4-ethynylphenyl)-9,9-bis(2-octyldodecyl)fluorene (7a) wasperformed under the same catalytic conditions as the small-molecular model reaction (Scheme 4a). The polyadditionreaction proceeded smoothly even at 30 °C and a low monomerconcentration of 0.02 M. The corresponding PAV (Paa) wasyielded in 96% yield with a number average molecular weight(Mn) of 41,000 and a polydispersity index (Mw/Mn) of 3.9. Allsignals in the 1H NMR spectrum of Paa were assigned to arepeating structure with a 1,2-vinylene unit and terminalstructures (Figure 3). No signal assignable to the 1,1-vinylideneunit was observed in the 1H NMR spectrum (5.5–5.0 ppm).Matrix-assisted laser desorption ionization time-of-flight massspectroscopy (MALDI-TOF-MS) confirmed the structure of therepeating and terminal units derived from each monomer (FigureS14). These results indicate that the hydroarylation of 5a with 7aproceeded with quantitative site- and regio-selectivity.Figure 3.1H NMR spectrum of Paa (600 MHz, C2D2Cl4, 373 K).The same molecular design is compatible with a C–Hmonomer consisting of a carbazole unit with 1-pyrazole directinggroups at the 3,6-positions (Scheme S2 and Figures S15–S17).The hydroarylation polyaddition of 9-(2-ethylhexyl)-3,6-di(1-pyrazolyl)carbazole (5c) with 2,7-bis(4-ethynylphenyl)-9,9-di(n-octyl)fluorene (7b) also gave the corresponding PAV (Pcb) in73% yield with an Mn of 11,000 and an Mw/Mn of 2.8 (Scheme4b). Moreover, the longer reaction time of the polyadditionreactions increased the molecular weight of Pcb; thepolyaddition reaction for 48 h gave Pcb in 71% yield with an Mnof 23,000 and an Mw/Mn of 3.4. Structural analyses of thesynthesized PAVs were conducted by NMR and MALDI-TOF-MS (Figures S18–S20). Almost all the signals in the 1H NMRand MALDI-TOF-MS spectra were assigned to each repeatingand terminal structure of the 1,2-vinylene unit, and 3–4% of the1,1-vinylidene unit was detected in the 1H NMR spectrum(Figures S18 and S19). Formation of the 1,1-vinylidene structurewas suppressed by changing the diyne monomer to less sterichindered 4,4’-diethynylbiphenyl (7c); the polyaddition reaction of5c with 7c proceeded over 99% of 1,2-vinylene selectivity in75% yield (Scheme S3, Figures S21 and S22). The molecularweight of Pcc could not be measured because Pcc wasinsoluble in THF.The optical properties of the synthesized monomers, modelproducts, and PAVs were investigated (Table 1). First, wecompared a series of naphthalene derivatives in CHCl3 solutions(5a, 6ab, and Paa). The ultraviolet-visible (UV-vis) absorptionand photoluminescence (PL) spectra are shown in Figure 4. Allthree molecules showed an absorption band at approximately300 nm due to π-π* transition of the 2,6-di(1-pyrazolyl)naphthalene core. The model product (6ab) had twoabsorption peaks at 302 and 361 nm. The longer-wavelengthabsorption at 361 nm was attributed to the conjugated mainchain of 3,7-naphthalenevinylene. The absorption maxima ofPaa was red-shifted compared with those of 5a and 6ab, whichwas caused by the π-extension. The PL spectra exhibited trends COMMUNICATION4similar to those observed in the absorption spectra. Theemission peaks of 5a, 6ab, and Paa were observed at 358, 425,and 460 nm, respectively. The intensities of the emission peaksof 6ab and Paa were much higher than those of 5a, which is dueto the rigid backbone of 3,7-naphthalenevinylene. Thephotoluminescence quantum yields (PLQY) of 6ab and Paa inCHCl3 solutions were estimated to be 84 and 80%, respectively.While the PLQY of the carbazole-based PAV (Pcb) in CHCl3solutions was slightly lower than that of the naphthalene-basedPAV (Paa); the optical spectra of Paa and Pcb are almostconsistent (Figure S31). In addition, the 1-pyrazole substituentdid not affect the absorption and PL properties, as supported bythe optical spectra and PLQY of the naphthalene- andcarbazole-based model compounds without 1-pyrazole groups(8a and 8b; Table S3 and Figure S32). The UV-vis absorptionand PL spectra in the film state were also evaluated (Table S3,Figures S33 and S34). While the absorption spectra wereconsistent with those in CHCl3 solutions, the PL spectra werered-shifted due to the intermolecular π-π stacking in the film states. The PLQY values in the film state decreased because ofaggregation-caused quenching (ACQ), [53,54] whereas Paa hademission properties as high as those of PAV for OLEDs. [55]Atomic force microscopy (AFM) and X-ray diffraction (XRD)analyses revealed that the spin-coated films of Paa and Pcbwere amorphous (Figure S35).Table 1. Optical properties of the monomer, model compounds, and PAVs.[a]Compound λabs [nm] λem [nm] PLQY [%][b]5a 267, 308 358 -6ab 302, 361 425 84Paa 405 460 80Pcb 406 454 66[a]Optical properties were measured in CHCl3 solution at concentrations of 5.0x 10-6M.[b]Photoluminescence quantum yield.Figure 4. Optical spectra of the naphthalene derivatives (monomer: 5a, modelproduct: 6ab, and PAV: Paa) in CHCl3 solutions (5.0 x 10-6M). (a) UV-visabsorption spectra. (b) PL spectra.Because the Paa film exhibited light-green emissions (λem =472 and 494 nm, quantum yield (φ) = 20%) when excited at 400 nm, the electroluminescent (EL) properties of Paa wereevaluated in OLED (Figure 5, see the Supporting Information forthe details of OLED fabrication). The EL spectrum was slightlyred-shifted from the PL spectrum because of the interferenceeffect between the emitted light that directly traveled from theemissive layer to the ITO electrode and the light that wasreflected once from the Al electrode. [56] The coordinates of theCIE chromaticity diagram were x = 0.285 and y = 0.451 at 1.43mA cm-2 (Figure S36). The luminance reached 323 cd m -2 at acurrent density of 80.4 mA cm-2, and the external quantumefficiency (EQE) of the OLED was 0.32% at 4.6 mA cm -2 (FigureS37). These results indicate that Paa serves as an emittingmaterial for OLEDs.Figure 5. (a) PL spectrum of the thin film of Paa and EL spectrum of theOLED using Paa and (b) Current density-voltage-luminance characteristics forthe fabricated OLED.In summary, naphthalene- and carbazole-based monomerswere designed via Co-catalyzed hydroarylation polyadditionunder mild conditions for the regiospecific synthesis ofpoly(arylenevinylene)s. The 1-pyrazole substituent was suitableas the directing group for the C–H activation of six-memberedaromatic rings. The introduction of the 1-pyrazole substituent atthe 2,6-positions of the naphthalene moiety was effective inselectively activating the C–H bonds at the 3,7-positions owingto the planar conformations of the 1-pyrazole substituents. Themolecular design of the aromatic monomer was versatile, notonly for the naphthalene unit but also for the carbazole unit. Thehydroarylation polyaddition of the designed naphthalene- andcarbazole-based monomers proceeded under mild conditions atroom temperature without producing by-products. Notably,hydroarylation polyaddition expands the C–H functionalizationstrategies for the synthesis of PAVs to generally inactive PAHmonomers. The synthesized PAVs showed a high PLQY andserved as emitting layers in OLEDs. Further molecular designsfor the synthesis of high-performance PAVs are currentlyunderway.AcknowledgementsThe authors thank the Chemical Analysis Division and theOPEN FACILITY, Research Facility Center for Science andTechnology, University of Tsukuba for the measurements ofNMR, X-ray crystallographic analyses, and MALDI-TOF-MS.This work was partly supported by JSPS KAKENHI GrantNumbers 23K04835 and 23KJ0240.COMMUNICATION5Conflict of interestThe authors declare no conflict of interest.Keywords: Cobalt • Hydroarylation • π-Conjugated polymer • Polyaromatic hydrocarbon • Organic light-emitting diode[1] J. Yamaguchi, A. D. Yamaguchi, K. Itami, Angew. Chem. Int. Ed.2012, 51, 8960–9009.[2] P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev. 2012, 112,5879–5918.[3] J. Wencel-Delord, F. Glorius, Nat. Chem. 2013, 5, 369–375.[4] T. Gensch, M. N. Hopkinson, F. Glorius, J. Wencel-Delord, Chem.Soc. Rev. 2016, 45, 2900–2936.[5] J. R. Hummel, J. A. Boerth, J. A. Ellman, Chem. Rev. 2017, 117,9163–9227.[6] L. Xing, C. K. Luscombe, J. Mater. Chem. C 2021, 9, 16391–16409.[7] J. Kuwabara, T. Kanbara, ChemPlusChem 2024, 89, e202300400.[8] L. G. Mercier, M. Leclerc, Acc. Chem. Res. 2013, 46, 1597–1605.[9] J. Kuwabara, T. Kanbara, Macromol. Rapid Commun. 2021, 42,2000493.[10] L. Ye, B. C. Thompson, J. Polym. Sci. 2022, 60, 393–428.[11] B. Z. Yongrui He, Lijun Huo, Nano Energy 2024, 123, 109397.[12] H. Aoki, H. Saito, Y. Shimoyama, J. Kuwabara, T. Yasuda, T.Kanbara, ACS Macro Lett. 2018, 7, 90–94.[13] C. Tanaka, J. Kuwabara, T. Yasuda, T. Kanbara, Synth. Met. 2019,254, 180–183.[14] N. Onda, R. Sato, J. Kuwabara, T. Yasuda, T. Kanbara, Synth. Met.2023, 293, 117279.[15] B. Chakraborty, C. K. Luscombe, Angew. Chem. Int. Ed. 2023, 62,e202301247.[16] G. Albano, Org. Chem. Front. 2024, 11, 1495–1622.[17] H. Saito, J. Kuwabara, T. Yasuda, T. Kanbara, Polym. Chem. 2016,7, 2775–2779.[18] H. Saito, J. Kuwabara, T. Yasuda, T. Kanbara, Macromol. RapidCommun. 2018, 39, 1800414.[19] J. Lee, H. J. Park, J. M. Joo, D.-H. Hwang, Macromol. Res. 2019,27, 115–118.[20] A. Kraft, A. C. Grimsdale, A. B. Holmes, Angew. Chem. Int. Ed.1998, 37, 402–428.[21] Y. Wang, T. Hasegawa, H. Matsumoto, T. Michinobu, J. Am. Chem.Soc. 2019, 141, 3566–3575.[22] C. Yang, S. Zhang, J. Hou, Aggregate 2022, 3, e111.[23] A. J. Blayney, I. F. Perepichka, F. Wudl, D. F. Perepichka, Isr. J.Chem. 2014, 54, 674–688.[24] H. G. Gilch, W. L. Wheelwright, J. Polym. Sci. Part A-1 Polym.Chem. 1966, 4, 1337–1349.[25] H. Becker, H. Spreitzer, K. Ibrom, W. Kreuder, Macromolecules1999, 32, 4925–4932.[26] R. N. McDonald, T. W. Campbell, J. Am. Chem. Soc. 1960, 82,4669–4671.[27] S. Pfeiffer, H. H. Hörhold, Synth. Met. 1999, 101, 109–110.[28] D. A. M. Egbe, H. Neugebauer, N. S. Sariciftci, J. Mater. Chem.2011, 21, 1338–1349.[29] H. Weychardt, H. Plenio, Organometallics 2008, 27, 1479–1485.[30] T. Haque, K. Nomura, Catalysts 2015, 5, 500–517.[31] V. P. Conticello, D. L. Gin, R. H. Grubbs, J. Am. Chem. Soc. 1992,114, 9708–9710.[32] S. W. Chang, M. Horie, Chem. Commun. 2015, 51, 9113–9116.[33] J. Dhar, T. Mukhopadhay, N. Yaacobi-Gross, T. D. Anthopoulos, U.Salzner, S. Swaraj, S. Patil, J. Phys. Chem. B 2015, 119, 11307–11316.[34] H. N. Cho, J. K. Kim, D. Y. Kim, C. Y. Kim, N. W. Song, D. Kim,Macromolecules 1999, 32, 1476–1481.[35] J. Pei, S. Wen, Y. Zhou, Q. Dong, Z. Liu, J. Zhang, W. Tian, New J.Chem. 2011, 35, 385–393.[36] T. Zhang, J. Wang, M. Zhou, L. Ma, G. Yin, G. Chen, Q. Li,Tetrahedron 2014, 70, 2478–2486.[37] H.-H. Horhold, J. Gottschaldt, J. Opferman, J. Prakt. Chem. 1977,319, 611–621.[38] S. Baysec, E. Preis, S. Allard, U. Scherf, Macromol. Rapid Commun.2016, 37, 1802–1806.[39] P. Klein, H. J. Jötten, C. M. Aitchison, R. Clowes, E. Preis, A. I.Cooper, R. S. Sprick, U. Scherf, Polym. Chem. 2019, 10, 5200–5205.[40] S. Selmani, L. Vanderzwet, A. J. Kukor, D. J. Schipper, Synlett 2018,29, 2552–2556.[41] R. Iwamori, R. Sato, J. Kuwabara, T. Yasuda, T. Kanbara,Macromol. Rapid Commun. 2021, 42, 2100283.[42] R. Iwamori, R. Sato, J. Kuwabara, T. Kanbara, Polym. Chem. 2022,13, 379–382.[43] R. Iwamori, J. Kuwabara, T. Yasuda, T. Kanbara, Macromolecules2023, 56, 5407–5414.[44] D. Lapointe, K. Fagnou, Chem. Lett. 2010, 39, 1118–1126.[45] L. Xing, J. R. Liu, X. Hong, K. N. Houk, C. K. Luscombe, J. Am.Chem. Soc. 2022, 144, 2311–2322.[46] R. Sato, T. Iida, T. Kanbara, J. Kuwabara, Chem. Commun. 2022,58, 11511–11514.[47] T. Mori, M. Kijima, Eur. Polym. J. 2009, 45, 1149–1157.[48] V. Sannasi, P. Manikandan, B. G. Sundararaj, M. T. Vijayan, D.Jeyakumar, Iran. Polym. J. 2010, 19, 969–981.[49] D. Wei, X. Zhu, J. L. Niu, M. P. Song, ChemCatChem 2016, 8,1242–1263.[50] M. Moselage, J. Li, L. Ackermann, ACS Catal. 2016, 6, 498–525.[51] T. Yoshino, S. Matsunaga, Adv. Synth. Catal. 2017, 359, 1245–1262.[52] B. Sun, T. Yoshino, M. Kanai, S. Matsunaga, Angew. Chem. Int. Ed.2015, 54, 12968–12972.[53] X. Ma, R. Sun, J. Cheng, J. Liu, F. Gou, H. Xiang, X. Zhou, J. Chem.Educ. 2016, 93, 345–350.[54] J.-H. Hsu, W. Fann, P.-H. Tsao, K.-R. Chuang, S.-A. Chen, J. Phys.Chem. A 1999, 103, 2375–2380.[55] E. W. Snedden, L. A. Cury, K. N. Bourdakos, A. P. Monkman, Chem.Phys. Lett. 2010, 490, 76–79.[56] T. Tsutsui, K. Yamamato, Jpn. J. Appl. Phys. 1999, 38, 2799–2803.COMMUNICATION6Entry for the Table of ContentsThe 1-pyrazole groups in 2,6-di(1-pyrazolyl)naphthalene adopt planar conformations and act as appropriate directing groups forgenerally inactive six-membered aromatic hydrocarbons, resulting in smooth hydroarylation reaction. The polyaddition reaction of 2,6-di(1-pyrazolyl)naphthalene selectively proceeds at 3,7-positions under mild reaction conditions of 30 °C, and yields correspondingpoly(arylenevinylene) with high molecular weight.