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Shoko Yoshida, Nozomi Kasakura, Miho Hirakawa, Hirofumi Morimoto, Kyohei Matsuo, [Hironobu Hayashi](https://orcid.org/0000-0002-7872-3052), [Mitsuaki Yamauchi](https://orcid.org/0000-0003-0005-5960), Ryutarou Kanamori, [Soji Shimizu](https://orcid.org/0000-0002-2184-7468), [Hiroko Yamada](https://orcid.org/0000-0002-2138-5902), [Naoki Aratani](https://orcid.org/0000-0002-3181-6526)

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[Well-Structured Narrow Near-Infrared Absorption Based on Nonaggregated Hexarylene-Bisimide toward a Colorless Dye](https://mdr.nims.go.jp/datasets/ad6fc874-96db-4b2f-a0f9-5ce2480dde22)

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Well-Structured Narrow Near-Infrared Absorption Based on Nonaggregated Hexarylene-Bisimide toward a Colorless DyeWell-Structured Narrow Near-Infrared Absorption Based onNonaggregated Hexarylene-Bisimide toward a Colorless DyePublished as part of The Journal of Organic Chemistry special issue “Physical Organic Chemistry: Never Out ofStyle”.Shoko Yoshida, Nozomi Kasakura, Miho Hirakawa, Hirofumi Morimoto, Kyohei Matsuo,Hironobu Hayashi, Mitsuaki Yamauchi, Ryutarou Kanamori, Soji Shimizu,* Hiroko Yamada,*and Naoki Aratani*Cite This: J. Org. Chem. 2025, 90, 15489−15494 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Extended π-conjugated systems are often insoluble,and their aggregation manner greatly affects their absorptionspectra. This study produced a planar, soluble, and nonaggregatedhexarylene-bisimide (HB) with appropriate substituents. Thesingle-crystal X-ray structure of HB confirmed the planar molecularstructure with small twist angles and the dimerization behavior ofHB in the solid state. The concentration-dependent 1H NMRexperiments in CDCl3 indicated that the association constant Kdimeris 4.6 × 103 M−1 at 298 K and ΔGdimer (298 K) = −20.8 kJ mol−1.The longest absorption of HB at the monomeric state exhibits asharp and intense peak at 921 nm (ε = 230,000 M−1 cm−1, fullwidth at half-maximum = 718 cm−1) in toluene. 75% of the absorption of HB above 400 nm appears in the near-infrared region, thusgiving a practically colorless solution. Magnetic circular dichroism spectra of a series of oligorylene-bisimides reveal the predominantcontribution of the linear polyene-like conjugation over the annulene-like conjugation for larger [n]oligorylene-bisimides.■ INTRODUCTION[n]Oligorylene is one of the representative polycyclic aromatichydrocarbons (PAHs) in which naphthalenes are linked at 1,8-positions to extend the π-conjugated system in a one-dimensional direction (Chart 1).1 Compared to higher acenes,the chemical stability of oligorylenes is remarkably high.2 Theabsorption spectra of [n]oligorylenes exhibit a red-shift due tothe effective π-conjugation and the reduction of the HOMO−LUMO gap as the number of n increases. As a result,hexarylene and higher are to be near-infrared (NIR) absorbingdyes.3 NIR absorbing dyes are applied in various fields such asoptical filters, security marking, etc.4 For these applications, itis important to have a large absorption coefficient (ε) in theNIR region (750−1100 nm) with no absorption in the visibleregion (380−750 nm), which makes the dye colorless,selectively NIR absorbent. Nevertheless, the properties of[n]oligorylenes with n ≥ 4 have rarely been investigated,because their solubility decreases with increasing molecularlength, making their synthesis and purification morechallenging.2 Therefore, in general, the bay-bridge alkylation5and the bay-area aryloxylation6 have been performed to ensurethe solubility and to extend the molecular length of[n]oligorylenes. However, introducing the solubilizing groupsinto the core skeleton intrinsically broadens their absorptionspectra due to the distortion of the backbone of theoligorylenes or strong aggregation behavior by the van derWaals interaction between long alkyl chains.5,6[n]Oligorylene-bisimides have electron-withdrawing imidegroups with chemical stability and n-type semiconductiveproperties (Chart 1). The absorption spectra of the long[n]oligorylene-bisimides are also broadened due to strongaggregation behavior and molecular distortion.7 Consequently,the absorption spectra significantly change from those of thepristine [n]oligorylene-bisimides. The aggregation-free [n]-oligorylene-bisimides with an undistorted skeleton should havesharper absorption spectra by suppressing the structuralfluctuations.8,9 Currently, the longest [n]oligorylene-bisimideever synthesized without distortion of the backbone bysubstituents is octarylene-bisimide (n = 8), the molecularstructure of which was confirmed only by scanning tunnelingmicroscopy because of its strong aggregation behavior.10Received: May 31, 2025Revised: September 22, 2025Accepted: October 17, 2025Published: October 27, 2025Articlepubs.acs.org/joc© 2025 The Authors. Published byAmerican Chemical Society15489https://doi.org/10.1021/acs.joc.5c01320J. Org. Chem. 2025, 90, 15489−15494This article is licensed under CC-BY-NC-ND 4.0Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on December 9, 2025 at 10:38:46 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/curated-content?journal=joceah&ref=featurehttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Shoko+Yoshida"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Nozomi+Kasakura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Miho+Hirakawa"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hirofumi+Morimoto"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kyohei+Matsuo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hironobu+Hayashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hironobu+Hayashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mitsuaki+Yamauchi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Ryutarou+Kanamori"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Soji+Shimizu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroko+Yamada"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naoki+Aratani"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naoki+Aratani"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acs.joc.5c01320&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/joceah/90/44?ref=pdfhttps://pubs.acs.org/toc/joceah/90/44?ref=pdfhttps://pubs.acs.org/toc/joceah/90/44?ref=pdfhttps://pubs.acs.org/toc/joceah/90/44?ref=pdfpubs.acs.org/joc?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acs.joc.5c01320?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/joc?ref=pdfhttps://pubs.acs.org/joc?ref=pdfhttps://acsopenscience.org/researchers/open-access/https://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/Müllen11a and Langhals11b also prepared planar hexarylene-bisimides (HBs), while the measurements of 1H NMR spectrawere unsuccessful due to the same reason. The objective of thisstudy is to establish a synthetic route to undistorted solubleHB fused with six naphthalene units and to seek an authenticabsorption spectrum of the HB. To prevent the distortion andto enhance the solubility at the same time, previously weprepared 2,6-bis-trifluoromethylphenyl-installed hexarylene(H, in Chart 1) and achieved a sharp absorption spectrumin the NIR region (831 nm in toluene, full width at half-maximum (fwhm) = 660 cm−1, ε = 131,000 M−1 cm−1).3b Inthis study, electron-withdrawing, sterically hindered 3,5-bis(trifluoromethyl)phenyl groups are installed into the centralbay area of the molecule. We expected that the electron-withdrawing groups stabilize the HOMO level, while the sterichindrance prevents intermolecular π-π stacking, achieving highsolubility and stability. As revealed in this study, the distortionof the molecular skeleton of HB due to the central aryl groupsis as small as 0.14° in the energy-minimized structure, resultingin the sharp absorption in the NIR region at 921 nm intoluene. On the other hand, we found that HB forms a discretedimer under highly concentrated conditions, which was provedby spectroscopic and X-ray crystallographic analysis.When the π-conjugation on the high-symmetry frameworkextends in one direction, the perfectly allowed transition to thefirst excited state (S0 → S1) in the NIR region will result in thefairly forbidden transition to the second excited state (S0 →S2) in the visible region so that the compound should becolorless. For this purpose, the sharpness of absorption bandsis also a noticeable key issue.■ RESULTS AND DISCUSSIONThe original synthetic route of a HB was developed by Müllenand co-workers.11a We slightly modified the conditions toimprove the yield of HB as shown in Scheme 1. Pure 1,7-dibromo-3,4,9,10-perylenetetra-carboxylic dianhydride12 wastransformed into bisimide 1 with cyclohexylamine in 78%yield. 1 and 3,5-bis(trifluoromethyl)phenyl boronic acid werecoupled by the Suzuki−Miyaura cross-coupling reaction in52% yield. Hydrolysis and decarboxylation reactions of 2 wereperformed to afford 1,7-disubstituted perylene 4 in 30% yieldin 2 steps.6a This perylene 4 was brominated with 2 equiv ofNBS to afford dibromoperylene 5 as a mixture of regioisomersin 89% yield. The Suzuki−Miyaura cross-coupling reaction of 5with 9-borylated perylene monoimide 613 gave a perylene triadin moderate yield. Hence, the reductive fusion reaction of thetriad was explored.11 To our delight, the treatment of the triadin ethanolamine in the presence of K2CO3 at 200 °C withmicrowave (MW) for 10 min led to the formation of fusionproduct HB in 44% yield after purification by silica gelchromatography.The structure of HB was confirmed by high-resolutionmatrix-assisted-laser-desorption/ionization time-of-flight (HR-MALDI-tof) mass spectrometry and 1H- and 13C NMRspectroscopy. HR-MALDI-tof mass spectrometry detectedthe parent ion peak at m/z = 1630.4514 (calcd. forC104H62N2O4F12 = 1630.4512 [M]+).The 1H NMR spectrum of HB in CDCl3 shows well-dissolved peaks at room temperature. Variable temperature 1HNMR measurements gave slightly sharper peaks at 50 °C thanthose at room temperature. The 1H NMR spectrum consists ofone singlet peak and ten doublet peaks for hexarylene protons,assigned by 2D-NMR (Supporting Information Figure S10).The proton peaks near the central unit, which were slightlybroad at room temperature, became sharper with increasingtemperature. This would be because the structural relaxationinduced by heating is the largest in the central area (vide infra).The single crystals suitable for X-ray diffraction analysis wereobtained by vapor diffusion of methanol into a solution of HBin toluene (Figures 1 and S23).14 In the crystal, twoindependent HB molecules are present in the unit cell, stackedChart 1. Chemical Structures of Oligorylenes, Hexaaryl-Hexarylene (H), and Oligorylene-Bisimides (PB−HB) inThis StudyScheme 1. Synthetic Route of Hexarylene-Bisimide HBaaArF = 3,5-bis(trifluoromethyl)phenyl.The Journal of Organic Chemistry pubs.acs.org/joc Articlehttps://doi.org/10.1021/acs.joc.5c01320J. Org. Chem. 2025, 90, 15489−1549415490https://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=cht1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=cht1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=sch1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=sch1&ref=pdfpubs.acs.org/joc?ref=pdfhttps://doi.org/10.1021/acs.joc.5c01320?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asparallel to the long axis with a mean-plane distance of 3.4 Å(Figure 1b). The hexarylene core is planar, with mean-planedeviations of 0.188 and 0.200 Å. The central core units areslightly tilted with dihedral angles of 14° and 23°. Theoptimized structure of HB calculated by density functionaltheory (DFT) (substituents on N atoms were replaced byhydrogen atoms) is nearly planar with a twist dihedral angle of0.14° at the center, as expected (Figure S26). These resultsindicate that HB exhibits some flexibility due to packing effectsin the crystal. As the outward-facing aryl groups becomehindered, this twisting is expected to restrict π-stackassociation up to dimerization, even if it is possible.Evidence of dimerization even in solution was obtained fromelectrospray ionization (ESI) mass spectrometry measure-ments of HB. As a result, dimer peaks were observed at m/z =3285.80676 (calcd. for C208H124N4O8F24Na = 3285.8995 [2M+ Na]+) (Figure S22). To check the dimerization behavior ofHB in the solution state, a concentration-dependent chemicalshift of HB in CDCl3 was traced via 1H NMR measurements.As an example, the chemical shift profiles of the proton peaksat 298 K are illustrated in Figure 2: the proton peaks originallyobserved at 8.06, 8.22, and 8.56 ppm were shifted to upfield at8.02, 8.03, and 8.30 ppm, respectively, due to the dimerization.The spectral features are analogous to those of othersupramolecular systems.15 These dimerization profiles (8samples, total data points N = 24) were analyzed with thecurve-fitting for binding systems (Figures S11−S16 and TablesS1−S3).16 Assuming that the dimer is in equilibrium, theequilibrium constants (Kdimer) were estimated to be 4.6, 2.1,and 1.6 × 103 M−1 at 298, 318, and 328 K, respectively. Thethermodynamic parameters (ΔH, ΔS, and ΔGdimer (298 K))were estimated at −27.4 kJ mol−1, −22 J K−1 mol, and −20.8kJ mol−1, respectively, from the van’t Hoff plots. From thesevalues, it is clear that the dominant formation of the dimer inthe equilibrium is attributable to the larger enthalpy term(TΔS < ΔH).The dimeric architecture of HB was further corroborated bydiffusion-ordered 2D-NMR spectroscopy (DOSY) in CDCl3.The 1H NMR signal at 2.8 ppm was with a diffusion coefficient(D) at 3.63 × 10−10 m2/s at [HB] = 7.3 × 10−4 M−1, which iscomparable to that of the bilayer nanographene17 (Mw =3829.49, D = 2.17 × 10−10 m2/s), suggesting the comparablemolecular weight. It should be noted that unlike bilayernanographene, which clearly forms a dimer in solution, HBexists in equilibrium between monomer and dimer in solution.The absorption spectrum of HB along with perylene-bisimide PB, terrylene-bisimide TB, quaterrylene-bisimide QB,and hexarylene H in toluene is shown in Figure 3. As expected,the maximum absorption wavelength was observed at 921 nm,and the molar absorption coefficient was 2.30 × 105 M−1 cm−1with an fwhm of 718 cm−1. The second and third vibrationalbands of the first electronic transition also have absorptionbands in the NIR region (818 and 740 nm), indicating that thecompound could be colorless in the solvent. 75% of theabsorption of HB above 400 nm appears in the NIR region. Bycomparing the absorption spectrum of HB with those of other[2]−[4]oligorylene-bisimides, it was experimentally revealedthat the absorption wavenumber (S0 → S1) becomes smallerproportional to the inverse of the molecular length and that theeffective conjugation length (ECL) continues to extendwithout saturation at least up to HB (Figure S25), as inoligorylenes.3b Since the plot of the energy gap versus theinverse of the number of repeating units is perfectly linear, weconsider an ideal model to be an electron in a one-dimensionalbox.11 Very interestingly, the intercepts are the same foroligorylene and oligorylene-bisimide (∼7,000 cm−1, 0.87 eV).This could indicate the intrinsic band gap of graphenenanoribbons ([5]GNRs), which is not affected by the substratesurfaces.18 The steady-state fluorescence of HB was notobserved like hexarylene.3bCyclic voltammetry (CV) measurements in CH2Cl2 wereperformed to investigate the redox properties of a series ofoligorylene-bisimides. The working, counter, and referenceelectrodes are glassy carbon, Pt wire, and Ag/AgNO3,respectively. With 0.1 M nBu4NPF6 as the electrolyte, thepotentials were determined based on the ferrocene/ferroce-nium (Fc/Fc+) couple. The results and values compared tothose of oligorylenebisimides are summarized in Figure 4 andTable S5. Reversible oxidation and reduction waves wereFigure 1. Single-crystal X-ray structure of HB. (a) Top view and (b)side view. Thermal ellipsoids are scaled at the 50% probability.Solvent molecules have been omitted for the sake of clarity.Figure 2. Concentration-dependent 1H NMR spectra (500 MHz) ofHB in CDCl3 at 298 K.The Journal of Organic Chemistry pubs.acs.org/joc Articlehttps://doi.org/10.1021/acs.joc.5c01320J. Org. Chem. 2025, 90, 15489−1549415491https://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig2&ref=pdfpubs.acs.org/joc?ref=pdfhttps://doi.org/10.1021/acs.joc.5c01320?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asobserved at 1.32, −0.98, and −1.40 V for PB, at 0.75 and−1.02 (2e−) V for TB, at 0.90, 0.45, and −0.96 (2e−) V forQB, and 0.46, 0.19, −0.98 (2e−), −1.74 and −1.99 V for HB,respectively. While the first oxidation potential (Eox1) shifts tothe negative side with the elongation of the molecular length,the first reduction potential (Ered1) remains unchanged for alloligorylenebisimides (ca. −1.0 V), and the two-electronreduction occurs for higher oligorylene-bisimides. Thus, thedifference in redox potentials (Eox1 − Ered1) eventuallydecreased as the molecular length became longer. Theseresults suggest that the oxidation is initiated at the center of themolecule, while the reduction occurs at the imide moieties atboth ends. These features showed good agreement with thecalculated electronic structures (Figure S24).To further give a detailed insight into the electronicstructures of a series of [n]oligorylene-bisimides, magneticcircular dichroism (MCD) spectra were measured (Figure5).19 PB exhibits the characteristic MCD signals as a perylene-Figure 3. (a) UV−vis-NIR absorption spectra of a series ofoligorylene-bisimides in toluene in wavelength unit. [HB] = 2.4 ×10−7 M−1. (b) UV−vis-NIR absorption spectra of H and HB inwavenumber unit. The inset shows photographs of HB solutions.Figure 4. Cyclic voltammogram of a series of oligorylene-bisimide inCH2Cl2 (IUPAC convention). [HB] = 6.0 × 10−5 M−1. The working,counter, and reference electrodes are glassy carbon, Pt wire, and Ag/AgNO3, respectively. With 0.1 M nBu4NPF6 as the electrolyte, thepotentials were determined based on the ferrocene/ferrocenium (Fc/Fc+) couple.Figure 5. MCD and absorption spectra of a series of oligorylene-bisimides in CH2Cl2.The Journal of Organic Chemistry pubs.acs.org/joc Articlehttps://doi.org/10.1021/acs.joc.5c01320J. Org. Chem. 2025, 90, 15489−1549415492https://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?fig=fig5&ref=pdfpubs.acs.org/joc?ref=pdfhttps://doi.org/10.1021/acs.joc.5c01320?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asbisimide derivative,20 a relatively weak positive Faraday B termcorresponding to the S0-to-S1 transition, followed by an intensenegative Faraday B term around 375 nm. In contrast to theintensification of the S0-to-S1 transition in the order PB, TB,QB, and HB, the corresponding MCD signals become lesssignificant in the same order and are nearly diminished in thecase of HB. The MCD signals arise from the Faraday effect dueto the interaction between the applied magnetic field and themagnetic dipole moments associated with the orbital motion ofelectrons, which is mainly contributed by the annulene-likeconjugation in the current case. The weaker MCD signalsobserved for the larger [n]oligorylene-bisimides, therefore,indicate the more significant contribution of the linearpolyene-like conjugation than the annulene-like conjugation,21which can be enhanced by the planar structure with negligibledistortion.■ CONCLUSIONSIn summary, we successfully synthesized 10,24-bis[3,5-bis-(trifluoromethyl)phenyl]hexarylene-bisimide HB using a re-ductive fusion reaction of the perylene triad. The product issoluble in common organic solvents and could be purified withcolumn chromatography. The optimized structure revealedthat the hexarylene core is not significantly disturbed by thesubstituents very much and is almost planar. We have shownthat HB is stacked and dimerized in the solid state and in highconcentration solutions, but we have also shown that HB ismonomeric under conditions where absorption spectra aremeasured, thus allowing us to measure the physical propertiesof HB in its discrete state. The longest absorption of HBexhibits a sharp peak at 921 nm in toluene with the fwhm of718 cm−1. The substituents did not perturb the electronicproperties of HB. The molecular coefficient is as large as230,000 M−1 cm−1, and 75% of the absorption bands of HBappear in the NIR region. Eventually, HB having lessabsorption at the visible light region was sufficiently stableunder the LED room light conditions for more than 1 week.The perfect straight line of the plots of the excitation energyand 1/n exhibits an ideal particle-in-a-box model. The physicalproperties of GNRs vary greatly depending on the edge state,length, and interaction with the substrate.17 Oligorylene-bisimide is the thinnest armchair graphene nanoribbon([5]AGNR), which is in a discrete form with a well-definedlength and substituents by solution synthesis, not on-surfacesynthesis, and is a valuable model for GNR. In total, wesucceeded in producing the NIR dye based on oligorylene,having no absorption peaks in the visible light region, and thesolution is almost colorless.■ ASSOCIATED CONTENTData Availability StatementThe data underlying this study are available in the publishedarticle and its Supporting Information.*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320.Synthetic procedures, NMR, MS, UV−vis spectroscopicdata, SCXRD results, and DFT calculation data (PDF)Accession CodesDeposition Number 2439975 contains the supplementarycrystallographic data for this paper. These data can be obtainedfree of charge via the joint Cambridge Crystallographic DataCentre (CCDC) and Fachinformationszentrum KarlsruheAccess Structures service.■ AUTHOR INFORMATIONCorresponding AuthorsSoji Shimizu − Department of Applied Chemistry, GraduateSchool of Engineering, and Center for Molecular Systems(CMS), Kyushu University, Fukuoka 819-0395, Japan;orcid.org/0000-0002-2184-7468; Email: ssoji@cstf.kyushu-u.ac.jpHiroko Yamada − Institute for Chemical Research, KyotoUniversity, Kyoto 611-0011, Japan; orcid.org/0000-0002-2138-5902; Email: hyamada@scl.kyoto-u.ac.jpNaoki Aratani − Division of Materials Science and MediluxResearch Center, Nara Institute of Science and Technology(NAIST), Ikoma 630-0192, Japan; orcid.org/0000-0002-3181-6526; Email: aratani@ms.naist.jpAuthorsShoko Yoshida − Division of Materials Science, Nara Instituteof Science and Technology (NAIST), Ikoma 630-0192,JapanNozomi Kasakura − Division of Materials Science, NaraInstitute of Science and Technology (NAIST), Ikoma 630-0192, JapanMiho Hirakawa − Division of Materials Science, Nara Instituteof Science and Technology (NAIST), Ikoma 630-0192,JapanHirofumi Morimoto − Division of Materials Science, NaraInstitute of Science and Technology (NAIST), Ikoma 630-0192, JapanKyohei Matsuo − Institute for Chemical Research, KyotoUniversity, Kyoto 611-0011, JapanHironobu Hayashi − Center for Basic Research on Materials,National Institute for Materials Science (NIMS), Tsukuba,Ibaraki 305-0047, Japan; orcid.org/0000-0002-7872-3052Mitsuaki Yamauchi − Institute for Chemical Research, KyotoUniversity, Kyoto 611-0011, Japan; orcid.org/0000-0003-0005-5960Ryutarou Kanamori − Department of Applied Chemistry,Graduate School of Engineering, and Center for MolecularSystems (CMS), Kyushu University, Fukuoka 819-0395,JapanComplete contact information is available at:https://pubs.acs.org/10.1021/acs.joc.5c01320Author ContributionsThe manuscript was written through the contributions of allauthors.NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThis work was supported by the Japan Society for thePromotion of Science (JSPS) KAKENHI Grant Nos.JP23K23332 (SS), JP24K01576 (HH), JP23K26480 (NA),JP25K01751 (HY), and JP20H05833 (Transformative Re-search Areas “Dynamic Exciton”), JST PRESTOJPMJPR21AC (HH), the CASIO SCIENCE PROMOTIONFOUNDATION (J41-23) funds, and the Masuyakinen basicresearch foundation. We thank Yoshiko Nishikawa (NAIST)The Journal of Organic Chemistry pubs.acs.org/joc Articlehttps://doi.org/10.1021/acs.joc.5c01320J. Org. Chem. 2025, 90, 15489−1549415493https://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/acs.joc.5c01320/suppl_file/jo5c01320_si_001.pdfhttps://summary.ccdc.cam.ac.uk/structure-summary?pid=ccdc:2439975&id=doi:10.1021/acs.joc.5c01320http://www.ccdc.cam.ac.uk/structureshttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Soji+Shimizu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-2184-7468https://orcid.org/0000-0002-2184-7468mailto:ssoji@cstf.kyushu-u.ac.jpmailto:ssoji@cstf.kyushu-u.ac.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroko+Yamada"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-2138-5902https://orcid.org/0000-0002-2138-5902mailto:hyamada@scl.kyoto-u.ac.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naoki+Aratani"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-3181-6526https://orcid.org/0000-0002-3181-6526mailto:aratani@ms.naist.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Shoko+Yoshida"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Nozomi+Kasakura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Miho+Hirakawa"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hirofumi+Morimoto"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kyohei+Matsuo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hironobu+Hayashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-7872-3052https://orcid.org/0000-0002-7872-3052https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mitsuaki+Yamauchi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-0005-5960https://orcid.org/0000-0003-0005-5960https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Ryutarou+Kanamori"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.joc.5c01320?ref=pdfpubs.acs.org/joc?ref=pdfhttps://doi.org/10.1021/acs.joc.5c01320?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asfor the MS measurements. We also thank Prof. Dr. ShoheiSaito, Dr. Akito Nakai (Kyoto University), and Shohei Katao(NAIST) for their help with the X-ray analysis. This work waspartly supported by the ARIM Program of the Ministry ofEducation, Culture, Sports, Science and Technology (MEXT)(JPMXP1225NR5003). H.M. is grateful to the NAIST SpecialFund and University Fellowships for Young Scientists.■ REFERENCES(1) (a) Markiewicz, J. T.; Wudl, F. Perylene, Oligorylenes, and Aza-Analogs. ACS Appl. Mater. Interfaces 2015, 7, 28063−28085.(b) Würthner, F.; Saha-Möller, C. R.; Fimmel, B.; Ogi, S.;Leowanawat, P.; Schmidt, D. Perylene Bisimide Dye Assemblies asArchetype Functional Supramolecular Materials. Chem. Rev. 2016,116, 962−1052.(2) Chen, L.; Li, C.; Müllen, K. Beyond perylene diimides: synthesis,assembly, and function of higher rylene chromophores. J. Mater.Chem. C 2014, 2, 1938−1956.(3) (a) Zhao, X.; Xiong, Y.; Ma, J.; Yuan, Z. 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