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Shoma Kasahara, [Hironobu Hayashi](https://orcid.org/0000-0002-7872-3052), Takayuki Okumura, [Michio Matsumoto](https://orcid.org/0000-0002-6037-0228), [Mitsuaki Yamauchi](https://orcid.org/0000-0003-0005-5960), [Yoshiyuki Mizuhata](https://orcid.org/0000-0001-5301-0024), [Naoki Aratani](https://orcid.org/0000-0002-3181-6526), [Hiroko Yamada](https://orcid.org/0000-0002-2138-5902)

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[Shape‐Persistent Anthracene‐Based Macrocycles Prepared by Reversible Boronic Ester Formation: Crystallization and Structural Analysis](https://mdr.nims.go.jp/datasets/d9b1af10-8c69-43e4-8e43-32245e1c74f4)

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Shape‐Persistent Anthracene‐Based Macrocycles Prepared by Reversible Boronic Ester Formation: Crystallization and Structural AnalysisVery Important PaperShape-Persistent Anthracene-Based Macrocycles Preparedby Reversible Boronic Ester Formation: Crystallization andStructural AnalysisShoma Kasahara,[a] Hironobu Hayashi,*[b] Takayuki Okumura,[c] Michio Matsumoto,[d]Mitsuaki Yamauchi,[a] Yoshiyuki Mizuhata,[a] Naoki Aratani,[c] and Hiroko Yamada*[a]Shape-persistent macrocycles with confined inner spaces havegained significant interest due to their unique properties andpotential applications in gas/molecular recognition, nanoscaletemplates, and nanoelectronics. In this study, we present anefficient synthesis of macrocycles containing anthracene unitsthrough reversible boronic ester formation between 1,2-diolsand boronic acids. These template-free macrocycles exhibiteddiverse internal cavities ranging from 11 Å to 20 Å and readilycrystallized in solution and on solid substrates. Powder X-raydiffraction analysis revealed that the crystallinity remained aftersolvent removal. Single crystal X-ray analysis provided detailedinsights into the molecular geometry and packing structure.Notably, a macrocycle with phenyl linkers resembles a pseudo-nanocapsule, as the bulky substituents on both sides of themacrocycles prevented the cavity filling by neighbouringmolecules. Consequently, the crystalline powders of the macro-cycle with phenyl linkers maintained its crystallinity even afterannealing, likely resulting in the highest N2 gas adsorptionproperties among synthesized macrocycles. This work high-lights a robust synthesis strategy for macrocycles, broadeningtheir potential for advanced applications and enabling self-assembled nanoarchitectures.IntroductionMacrocycles with confined inner space have gained significantattention because they often exhibit specific property depend-ing on the structure and size of cavity.[1–7] Specifically, shapepersistent macrocycles have been regarded as importantmaterials for gas/molecular recognition, which contributes toseparate or storage desired materials from a mixture ofproducts.[1,3–16] Additionally, accumulating crystalline or self-assembled macrocycles on a substrate in an orderly mannerthrough solution process, they can be utilized as nanoscaletemplates or patterning materials, and can also be used in thefabrication of nanoelectronics devices and the design of circuitsat the nanometer scale.[17–21] These properties and applicationsare influenced by the size and shape of the cavities as well asthe electronic feature of organic moieties. Therefore, toenhance and diversify these properties, it is essential to developefficient methods for synthesizing macrocycles with variousshapes and cavity size with crystalline nature. In spite of theseattractive features of macrocycles, the reaction yields of macro-cyclization are often low, because of the competing undesirablepolymerization.[22,23]The utilization of dynamic covalent bond offers a promisingway for the selective formation of desired structure bycontrolling the reaction equilibrium.[24–35] Specifically, boronicesters can be readily synthesized by mixing boronic acids withalcohols such as 1,2- and 1,3-diol.[9,34,35] This reversible reactionhas been employed to construct not only macrocycles but alsocomplex structures such as molecular organic cages,[36–41]covalent organic frameworks (COFs), and two-dimensionalporous nanosheets.[42]Herein, we present the efficient synthesis of a set of shape-persistent macrocycles containing anthracene units, utilizingreversible boronic ester formation between 1,2-diols andboronic acids. Anthracene derivatives, which possess rigid andplanar structures with high air stability, show reasonablesolubility together with easy chemical modification to tune thepacking structure.[43–45] Additionally, anthracene and its deriva-tives were utilized as building blocks for the construction ofmacrocyclic arenes.[46,47] The macrocycles were synthesized with-out the use of any template molecules, with a variety of internalcavities depending on organic linker molecules. These macro-cycles readily crystallized in liquid phase and on substrates. Thecrystallinity was maintained after solvent removal. Finally, we[a] S. Kasahara, Dr. M. Yamauchi, Prof. Dr. Y. Mizuhata, Prof. Dr. H. YamadaInstitute for Chemical ResearchKyoto UniversityGokasho, Uji, Kyoto 611-0011, JapanE-mail: hyamada@scl.kyoto-u.ac.jp[b] Dr. H. HayashiCenter for Basic Research on MaterialsNational Institute for Materials Science (NIMS)1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, JapanE-mail: HAYASHI.Hironobu@nims.go.jp[c] T. Okumura, Prof. Dr. N. ArataniDivision of Materials ScienceNara Institute of Science and Technology (NAIST)8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan[d] Dr. M. MatsumotoInternational Center for Nanoarchitectonics (MANA)National Institute for Materials Science (NIMS)1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanSupporting information for this article is available on the WWW underhttps://doi.org/10.1002/cplu.202500014Wiley VCH Donnerstag, 01.05.20252551 / 400581 [S. 484/489] 1ChemPlusChem 2025, 90, e202500014 (1 of 6) © 2025 Wiley-VCH GmbHChemPlusChemwww.chempluschem.orgResearch Articledoi.org/10.1002/cplu.202500014http://orcid.org/0000-0002-7872-3052http://orcid.org/0000-0002-6037-0228http://orcid.org/0000-0003-0005-5960http://orcid.org/0000-0001-5301-0024http://orcid.org/0000-0002-3181-6526http://orcid.org/0000-0002-2138-5902https://doi.org/10.1002/cplu.202500014http://crossmark.crossref.org/dialog/?doi=10.1002%2Fcplu.202500014&domain=pdf&date_stamp=2025-04-04investigated the surface areas of obtained crystalline powdersbased on the gas adsorption.Results and DiscussionThe general synthetic scheme for macrocycles was shown inFigure 1. Firstly, an anthracene derivative, Ant-OH, with twosets of fixed cis-1,2-diol units positioned on the same face of anearly planar anthracene framework was specifically designed.The orientation of these two sets of fixed cis-1,2-diol units isreasonable for the macrocyclization with diboronic acidderivatives.[9,34,35] Triisopropylsiliy(TIPS)ethynyl groups were in-troduced at the 9,10-positions of anthracene. The presence ofTIPSethynyl groups on both sides of the macrocycles ensuressolubility and influences tuning the packing structure of thecrystals.[48]The isomeric mixture of cis-1,2-diol was synthesized, follow-ing Scheme S1.[49] To achieve macrocyclization, it was necessaryto separate Ant-OH with bis(cis-1,2-diol) from its isomericmixture. Due to the similar polarity, separating the isomers viasilica gel column chromatography was challenging. However, itwas discovered that the differences in the solubility in chloro-form enabled the successful isolation of bis(cis-1,2-diol) fromthe mixture by simply washing with chloroform. Attempts tocrystallize the separated Ant-OH yielded only plate-like crystals,which were unsuitable for single-crystal X-ray analysis. As aresult, Ant-OH was further reacted with phenyl boronic acid toproduce Ant-Ph (Figure 2). Needle-shaped crystals of Ant-Phwere successfully obtained through slow diffusion in chloroformwith 2-propanol vapor. Single crystal X-ray analysis confirmedthe formation of boronic esters, demonstrating that the bis(cis-1,2-diol) group of Ant-OH reacted with phenyl boronic acid inthe desired orientation.[50] Consequently, this structure of Ant-Ph proved the successful isolation of the desired Ant-OH (viceversa).The macrocyclization of Ant-OH with various of diboronic acidderivatives was investigated (Figure 3, Scheme S1). For instance,Ant-OH and slight excess molar amount of 4,4'-biphenyldiboronicacid were mixed in methanol at room temperature. This mixtureled to the formation of precipitates immediately, which wereinsoluble in methanol. Indeed, matrix-assisted-laser-desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)analysis indicated that macrocycles were rapidly formed within10 min (Figure S1). After collecting the precipitates by filtration,the 1H NMR spectrum of this crude material suggested that theobtained precipitates contained BiPh[2+2] as the main product.However, linear polymetric boronic esters composed of Ant-OHand 4,4'-biphenyldiboronic acid, which exhibited broad 1H NMRpeaks, needed to be removed (Figure S6). Interestingly, theformation of large macrocycles such as BiPh[3+3] were alsoobserved in MALDI-TOF MS spectra of crude solution, althoughthe intensity of these peaks was quite weak. In fact, BiPh[3+3]was a minor species regardless of trying the macrocyclization withtemplates or different solvents,[35,51] as confirmed by the separationwith gel permeation chromatography (GPC) (vide infra), and itcould not be isolated. These results suggest that [2+2] macro-cycles appear to be thermodynamically stable, justified by the factthat forming a [3+3] cyclic structure leads to a significantly largedihedral angle in the 1,2-diol groups introduced at the termini ofanthracene, making such a cyclic structure unfavorable. Further-more, the synthesis of [3+3] cyclic structures with similarprecursors containing 1,2-diol groups can be selectively achievedusing specific molecules/solvents as templates.[35] Finally, the crudematerial containing BiPh[3+3] and undesirable polymers waspurified by GPC, giving pure BiPh[2+2] in 77% yield. Similarly,the combination of Ant-OH with various diboronic acids success-fully provided a series of macrocycles such as Ph[2+2] (43%yield), TerPh[2+2] (83% yield), Py[2+2] (87% yield), and TT[2+2] (75% yield) (Figure 3).This macrocyclization reaction requires a protic solvent,specifically methanol. It was reported that transesterificationtakes place through a borate intermediate formed by thecoordination between methanol and the boron atom of theFigure 1. General synthesis for macrocycle employed in this study.Figure 2. Synthesis of Ant-Ph and single crystal X-ray structure of Ant-OH.The thermal ellipsoids are shown at 50% probability. Hydrogen atoms andsolvent molecules were removed for the clarity. Reaction condition: a)Phenylboronic acid, MeOH, room temperature, 88%. Figure 3. A set of macrocycles synthesized in this study.Wiley VCH Donnerstag, 01.05.20252551 / 400581 [S. 485/489] 1ChemPlusChem 2025, 90, e202500014 (2 of 6) © 2025 Wiley-VCH GmbHChemPlusChemResearch Articledoi.org/10.1002/cplu.202500014 21926506, 2025, 5, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202500014 by National Institute For, Wiley Online Library on [26/06/2025]. 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 Licensemolecule.[51] To confirm the formation of macrocycles viareversible transesterifications with reasonable yields, the ex-change reaction was attempted. Briefly, BiPh[2+2] and tenequivalent amounts of pyrene-2,7-diboronic acid were mixed ina mixture of methanol/chloroform (9 :1), and stirred for severalhours at room temperature. The MALDI-TOF MS spectrum ofthe reaction mixture clearly showed the formation of Py[2+2],resulting from the dissociation and subsequent re-bonding ofthe boronic ester units of dissociated species of BiPh[2+2]with the 1,2-diol groups of pyrene-2,7-diboronic acid (Figure 4).The observation of macrocycle [1+2+1], comprising pyreneand biphenyl groups, provides additional evidence for thereversible transesterifications. Here, the intensity of MALDI-TOFMS spectrum does not accurately reflect the quantities ofproducts in the system. Note that the formation of precipitatesfacilitated the isolation of the macrocycle from the system. It isnoteworthy that the intermediates of the macrocycle and shortlinear oligomers exhibit better solubility in methanol than themacrocycle due to the terminal OH groups, which alsopromotes the transesterification.Next, the stability of these macrocycles was investigated.Although dynamic covalent bonding is essential for the formationof these macrocycles, 1H NMR measurements and MALDI-TOF-MSrevealed that all macrocycles are quite stable once formed insolution. For example, the 1H NMR spectra of BiPh[2+2] in CDCl3showed no significant changes after 48 hours, indicating that thestability of BiPh[2+2] (Figure S11). However, the macrocyclesgradually decomposed in the presence of bases such as triethyl-amine, as amine molecules bind to boronic esters.[9] Additionally,the stability in the solid state was also examined. Thermogravi-metric analysis (TGA) revealed that all prepared macrocyclesshowed no significant weight loss below 300°C, suggesting goodthermal stability (Figure S12).The optical properties of the macrocycles were examined.UV-vis absorption spectra of the macrocycles in THF are shownin Figure 5. The well-resolved absorption bands of anthracenewere clearly observed for macrocycles at 390, 417, and 442 nm,closely matching those of Ant-OH, and therefore the macro-cyclization gave no effect on the electronic states of anthra-cenes and organic linker molecules. In addition, the molarextinction coefficients (ɛ) of the macrocycles were approx-imately twice the values. These results indicate that there is nospecific interaction between the anthracene and the linker unitsin the ground state. A similar trend was observed in thefluorescence spectra in solution (Figure S13). These macrocyclesreflect the good fluorescence feature of Ant-OH, with thefluorescence maxima at 511 nm and quantum yields (Φf)ranging from 0.82 to 0.84 (Table S1). The fluorescence lifetimewas comparable to that of Ant-OH (5.4–5.5 ns) (Figure S14).To gain insight into the molecular geometry in the solid state,single-crystal X-ray analysis was performed (Figure 6). Thesemacrocycles were readily crystallized, although the crystallizationrequired different solvent systems. In all cases, the inner spaces ofmacrocycles were filled with solvent molecules, while somesolvent molecules also occupied the outer spaces of the macro-cycles. For instance, in the case of Ph[2+2], the crystal wasobtained through the slow evaporation of methanol into an o-dichlorobenzene solution of Ph[2+2]. Two o-dichlorobenzenemolecules were packed in the inner space of Ph[2+2] (Fig-ure S15). Interestingly, the anthracene backbone was slightlybended (Figure 6a), likely because the boronic ester units of Ph[2+2] needed to be flat against the phenyl units in the linker part,causing the anthracene to release strain by bending. In thepacking structure, the 5-membered rings containing boronic esterinteracted with those in the neighboring macrocycle (closestC***B distance of 3.4 Å). Additionally, the C2H4 bridge ofbicyclo[2.2.2]octane moieties, tethered on both sides of theanthracene unit, interacted with anthracene units of the neighbor-ing Ph[2+2] through CH–π interactions. These CH–π interactionsgave the two-dimensional nanosheet of Ph[2+2]. BiPh[2+2] andTerPh[2+2] also interacted in a similar manner to Ph[2+2]. Therelatively large inner spaces of BiPh[2+2] and TerPh[2+2]accommodated the TIPS units to pack BiPh[2+2] or TerPh[2+2],forming the one-dimensional alignment of macrocycles. In thecase of TerPh[2+2], the anthracene backbone was almost flat,probably because the central phenyl units of terphenyl linkerreleased the strain on the macrocycles, while the linker of BiPh[2+2] remained bend. Crystals of TT[2+2] suitable for single crystalX-ray analysis were not obtained. Although the quality of crystalsfor Py[2+2] was also not suitable for single crystal X-ray analysis,the preliminary structure and packing could be discussed (Fig-Figure 4. MALDI-TOF-MS spectrum for exchange reactions. Insets shows themagnified region of MALDI-TOF-MS spectrum.Figure 5. UV-vis absorption spectra of macrocycles in THF.Wiley VCH Donnerstag, 01.05.20252551 / 400581 [S. 486/489] 1ChemPlusChem 2025, 90, e202500014 (3 of 6) © 2025 Wiley-VCH GmbHChemPlusChemResearch Articledoi.org/10.1002/cplu.202500014 21926506, 2025, 5, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202500014 by National Institute For, Wiley Online Library on [26/06/2025]. 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 Licenseure S16). The size of the inner space is almost the same as that ofBiPh[2+2] due to the same length of pyrene-2,7-diboronic acidand 4,4'-biphenyldiboronic acid. Overall, by changing the linkerunits, the “width” of macrocycles varied from 11 Å to 20 Å,indicating that these macrocycles can potentially uptake differentmolecules, depending on the tunable inner size.The solubility of macrocycles appears to be primarilydetermined by the size of the inner voids and the presence ofbulky TIPS units on both sides of the macrocycles. In fact, thesolubilities of Ph[2+2], BiPh[2+2], and TerPh[2+2] in chloro-form are as follow: 0.12 mg/ml for Ph[2+2], 0.17 mg/ml forBiPh[2+2], and 0.40 mg/ml for TerPh[2+2]. Space-filling modelsfor these macrocycles visualized the spaces where solventmolecules might penetrate (Figure S17), supporting that solventmolecules find it difficult to reach the inner space easily, therebydecreasing the solubility, especially in the case of Ph[2+2]. Thus,because of the bulky TIPS groups on both sides of the macro-cycles, Ph[2+2] can be classified as resembling a pseudo-nano-capsule.The activated crystals of macrocycles were prepared byrecrystallization and filtration, followed by drying under vacuum at100°C for 3 h. Powder X-ray diffraction (PXRD) analysis revealedthat macrocycles maintained their crystallinity after solventremoval (Figure S18). According to the single-crystal X-ray struc-ture analysis, before activating of the macrocycles by heating, theinner cavities of BiPh[2+2] and TerPh[2+2] were occupied notonly by solvent molecules but also by TIPS groups of theneighboring macrocycles, which were positioned to fill the voidswithin the cavities. Upon filtration and annealing, the solventmolecules in the cavities were removed. This increased thefreedom of the TIPS groups of macrocycles, leading to arearrangement of the packing structure and reducing the usableinner cavities. In fact, prolonged annealing or annealing at 120°Cresulted in broadened PXRD patterns for the crystalline powdersof BiPh[2+2] and TerPh[2+2] (Figure S18), suggesting dimin-ished crystallinities. Conversely, the space-filling model of Ph[2+2] clearly shows that TIPS groups of neighboring Ph[2+2]macrocycles are unable to fill the inner cavities of a Ph[2+2],because of its short linkers (i.e. phenyl linkers) and bulky TIPSgroups. Consequently, in the case of Ph[2+2], the removal ofsolvent molecules mainly occurs upon the filtration and annealing,preserving its crystallinity. This prevents significant change uponsolvent removal and annealing, as evidenced by sharp PXRDpattern observed even after annealing at 140°C —a stark contrastto BiPh[2+2] and TerPh[2+2] (Figure S18), highlighting itspseudo-nanocapsule-like nature. Interestingly, the macrocyclesreadily crystallized on a Si/SiO2 surface or a glass substrate simplyby drop-casting the solution of macrocycles (Figure 7). Thechanging of interfacial color in the polarized optical microscopeFigure 6. Single crystal X-ray structures of (a,b) Ph[2+2], (e,f) BiPh[2+2], and (i,j) TerPh[2+2]. Packing structure of (c,d) Ph[2+2], (g,h) BiPh[2+2], and (k,l)TerPh[2+2]. The thermal ellipsoids are shown at 50% probability. Solvent molecules and hydrogen atoms are omitted for clarity.Figure 7. Typical POM images of crystals of BiPh[2+2] on a Si/SiO2 surface.Concentrations for drop-casting of THF solution: 50 μM.Wiley VCH Donnerstag, 01.05.20252551 / 400581 [S. 487/489] 1ChemPlusChem 2025, 90, e202500014 (4 of 6) © 2025 Wiley-VCH GmbHChemPlusChemResearch Articledoi.org/10.1002/cplu.202500014 21926506, 2025, 5, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202500014 by National Institute For, Wiley Online Library on [26/06/2025]. 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 License(POM) images indicated the crystallinity of formed needle-likestructure.The crystallinity of macrocycles encouraged us to evaluatetheir potential application as gas adsorbents. The macrocycles(Ph[2+2], BiPh[2+2], and TerPh[2+2]) were crystallized andthen filtered followed by drying at 100°C for 12 hours undervacuum. Then, N2 sorption isotherms for obtained crystallinepowders of macrocycles were measured up to 1 atm at 78 K(Figure 8). Note that our system lacks precision at low relativepressures (P/P0 < ~0.1). Because of this uncertainty, we assumedthat the Brunauer–Emmett–Teller (BET) model could be applied tothe N2 gas adsorption isotherm of Ph[2+2] for P/P0 ranging from0.155 to 0.245. This approach yielded an apparent surface area ofBET=108 m2/g (Figure 8, S19). Although this value is modestcompared to typical porous materials such as COFs,[42,52] it fallswithin the range of other arene-based crystalline macrocycles,[53]even though some of which were nonporous (0.9–5.0 m2/g).[54–57]Interestingly, the BET surface area of macrocycles likely increasedas the size of inner cavity decreased. The BET surface areas ofPh[2+2], BiPh[2+2], and TerPh[2+2] are as follow: 108 m2/g forPh[2+2], 45 m2/g for BiPh[2+2], and 35 m2/g for TerPh[2+2].Notably, Ph[2+2] clearly exhibited the highest value among thesemacrocycles. It was initially expected that as the size of the innercavities of the macrocycles increased, the number of adsorptionsites would also increase, thereby leading to a larger BET surfaceare. However, the results indicated the opposite trend. Based onthe single-crystal X-ray structures and PXRD analyses, the followingreasons can be considered. As the linkers of the macrocyclesbecome longer, the macrocycles exhibit increased flexibility. ForPh[2+2], the pseudo-nanocapsule-like structure prevents loss ofadsorption sites upon solvent removal, whereas BiPh[2+2] andTerPh[2+2] undergo packing structure rearrangements, reducingavailable cavities. Consequently, these factors account for Ph[2+2] exhibiting larger BET surface area compared to BiPh[2+2] andTerPh[2+2].ConclusionsIn summary, we have successfully synthesized a series of shape-persistent macrocycles containing anthracene units throughdynamic covalent bond formation between 1,2-diols andboronic acids. These macrocycles, synthesized without the useof template molecules, feature various internal cavity sizesranging from 11 Å to 20 Å, and crystallized readily both insolution and on solid substrates. The crystalline nature of themacrocycles was maintained even after solvent removal. Single-crystal X-ray analysis provided insights into the moleculargeometry and packing structures. For example, the C2H4 bridgeof bicyclo[2.2.2]octane moieties in Ph[2+2] interacted withanthracene units of the neighboring macrocycles through CH–πinteractions. Additionally, Ph[2+2] resembles a pseudo-nano-capsule because of its short linkers and the presence of bulkyTIPS groups on both sides of the macrocycles. This config-uration prevents significant changes of the packing structureupon solvent removal and annealing, which is in stark contrastto BiPh[2+2] and TerPh[2+2], where the packing rearrange-ment occur, reducing usable inner cavities. These findingsindicate the crucial role of TIPS groups and linker lengths indetermining the usable cavity space, likely accounting for Ph[2+2] possessing better N2 sorption property compared toBiPh[2+2] and TerPh[2+2].Overall, this work demonstrates an efficient synthesisstrategy for synthesizing stable and tunable macrocycles.Notably, the TIPS groups on both sides of the macrocycles offera significant advantage: desilylation followed by couplingreactions such as Sonogashira reactions can introduce variousfunctional groups. This approach not only enables the creationof valuable macrocycles with diverse functional groups but alsoopens the possibility for constructing organized self-assemblednanoarchitectures, foldamers, molecular machines, and artificialion channels.[9,58–62]Supporting InformationThe authors have cited an additional reference within theSupporting Information (Ref. [63]). The Supporting Informationincludes full details of synthesis, additional spectra, details ofdata collections. Deposition Numbers 2412652 (for Ant-Ph),2412655 (for Ph[2+2]), 2412656 (for BiPh[2+2]), and 2412657(for TerPh[2+2]) contain the supplementary crystallographicdata for this paper. These data are provided free of charge bythe joint Cambridge Crystallographic Data Centre and Fachin-formationszentrum Karlsruhe Access Structures service.AcknowledgementsThis work was partly supported by JST PRESTO grant No.JPMJPR21AC (HH), JSPS KAKENHI grant Nos. JP20H02816 (HH),JP24K01576 (HH), JP23K26480 (NA), and JP20H05833 (HY), ARIMof MEXT (JPMXP1224NM5302 and JPMXP1224NR5025), JST, theestablishment of university fellowships towards the creation ofFigure 8. N2 gas adsorption-desorption isotherm of (a) Ph[2+2], (b) BiPh[2+2], and (c) TerPh[2+2].Wiley VCH Donnerstag, 01.05.20252551 / 400581 [S. 488/489] 1ChemPlusChem 2025, 90, e202500014 (5 of 6) © 2025 Wiley-VCH GmbHChemPlusChemResearch Articledoi.org/10.1002/cplu.202500014 21926506, 2025, 5, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202500014 by National Institute For, Wiley Online Library on [26/06/2025]. 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 Licensehttps://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/cplu.202500014https://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/cplu.202500014https://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/cplu.202500014http://www.ccdc.cam.ac.uk/structuresscience technology innovation, grant No. JPMJFS2123 (SK), andJST SPRING, grant No. JPMJSP2110 (SK). We thank Shohei Katao(NAIST) for X-ray crystallographic analysis, Dr. Atsuro Takai(NIMS) for TGA, and Chie Negoro (NIMS) for compoundpurification.Conflict of InterestsThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are availablefrom the corresponding author upon reasonable request.Keywords: macrocycle · reversible bond formation · crystal ·porous material · anthracene[1] Y. Wang, H. Wu, J. F. Stoddart, Acc. Chem. Res. 2021, 54, 2027–2039.[2] M. Iyoda, J. Yamakawa, M. J. Rahman, Angew. Chem. Int. Ed. 2011, 50,10522–10553.[3] D. Talukdar, J. M. Kumar, B. Gole, Cryst. Growth Des. 2023, 23, 7582–7611.[4] T. Ogoshi, T. A. Yamagishi, Y. Nakamoto, Chem. Rev. 2016, 116, 7937–8002.[5] G. W. Gokel, W. M. Leevy, M. E. Weber, Chem. Rev. 2004, 104, 2723–2750.[6] I. Roy, A. H. G. David, P. J. Das, D. J. Pe, J. F. Stoddart, Chem. Soc. Rev.2022, 51, 5557–5605.[7] X. N. Han, Y. Han, C. F. Chen, Chem. Soc. 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Ed. 2006, 45, 4416–4439.Manuscript received: January 9, 2025Revised manuscript received: February 25, 2025Accepted manuscript online: March 2, 2025Version of record online: April 4, 2025Wiley VCH Donnerstag, 01.05.20252551 / 400581 [S. 489/489] 1ChemPlusChem 2025, 90, e202500014 (6 of 6) © 2025 Wiley-VCH GmbHChemPlusChemResearch Articledoi.org/10.1002/cplu.202500014 21926506, 2025, 5, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202500014 by National Institute For, Wiley Online Library on [26/06/2025]. 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 License Shape-Persistent Anthracene-Based Macrocycles Prepared by Reversible Boronic Ester Formation꞉ Crystallization and Structural Analysis Introduction Results and Discussion Conclusions Supporting Information Acknowledgements Conflict of Interests Data Availability Statement