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Yuto Maruyama, [Biplab Manna](https://orcid.org/0000-0002-7619-7765), [Koji Harano](https://orcid.org/0000-0001-6800-8023), Hayato Kanai, Yasuhiro Ishida, [Hiromitsu Maeda](https://orcid.org/0000-0001-9928-1655)

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[Multidirectionally Controlled Arrangement via Ion‐Pairing Assembly of Amphiphilic Charged π‐Electronic Systems](https://mdr.nims.go.jp/datasets/93c6f3e3-f31e-462a-afb1-df8ec831b3fe)

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Multidirectionally Controlled Arrangement via Ion‐Pairing Assembly of Amphiphilic Charged π‐Electronic SystemsRESEARCH ARTICLEwww.small-journal.comMultidirectionally Controlled Arrangement via Ion-PairingAssembly of Amphiphilic Charged 𝝅-Electronic SystemsYuto Maruyama, Biplab Manna, Koji Harano, Hayato Kanai, Yasuhiro Ishida,and Hiromitsu Maeda*Charged 𝝅-electronic systems with hydrophilic substituents form lyotropicchromonic liquid crystals (LCLCs) through charge-by-charge assemblydriven by i𝝅–i𝝅 interactions and hydrophobic effects. In this study,the positions and numbers of triethylene glycol (TEG) chains in amphiphilicporphyrin AuIII complexes are tuned to control their assembly modes.In combination with the 𝝅-electronic anion pentacyanocyclopentadienide(PCCp–), 5,15-TEG-aryl-substituted porphyrin AuIII complex generateslamello-columnar (Lamcol) phases via amphiphilic i𝝅–i𝝅 interactionsand proximal interactions at the unsubstituted sites. In the presence ofwater, the Lamcol phases, with lateral hydrophobic effects, exhibit transitionsto nematic sheet (Nsheet) and isotropic sheet (Isosheet) phases dependingon water content and temperature. The Lamcol phases align macroscopicallyunder a magnetic field, and scanning transmission electron microscopy(STEM) reveals monolayer sheet structures as key components of theLCLCs. These findings demonstrate a controllable charge-by-charge strategyfor designing 𝝅-electronic LCLCs with tunable structural and phase behaviors.Y. Maruyama, H. MaedaDepartment of Applied ChemistryCollege of Life SciencesKusatsu 525–8577, JapanE-mail: maedahir@ph.ritsumei.ac.jpB.Manna, K.HaranoCenter for Basic ResearchonMaterialsNational Institute forMaterials ScienceTsukuba 305–0044, JapanK.HaranoResearchCenter for AutonomousSystemsMaterialogy (ASMat)Institute of IntegratedResearchInstitute of ScienceTokyoYokohama226–8501, JapanH.Kanai, Y. IshidaCenter for EmergentMatter Science (CEMS)RIKENWako351–0198, JapanThe ORCID identification number(s) for the author(s) of this articlecan be found under https://doi.org/10.1002/smll.202511729© 2025 The Author(s). Small published by Wiley-VCH GmbH. This is anopen access article under the terms of the Creative Commons AttributionLicense, which permits use, distribution and reproduction in anymedium, provided the original work is properly cited.DOI: 10.1002/smll.2025117291. IntroductionIn supramolecular polymers,[1–13] includ-ing fibers, ribbons, tubes, sheets, cap-sules, and 3D networks, building blocksare assembled via noncovalent interactions,such as hydrogen-bonding, van der Waals,and 𝜋–𝜋 interactions, along with solvo-phobic effects. Rational molecular designenables precise control over the size andshape of nanostructures. In 𝜋-electronicsystems, 𝜋–𝜋 interactions among the coreunits induce the formation of colum-nar structures. Multi-directional interac-tions among 𝜋-electronic systems can con-trol the arrangement of columns in nanos-tructures and their organized structures(Figure 1a). In addition, structural featuresof assemblies are influenced by molec-ular geometries and the relative ratiosof hydrophilic to hydrophobic parts.[14–16]In amphiphilic 𝜋-electronic systems, as-sembly in the lateral direction of the𝜋-planes occurs via hydrophobic effects at sites lacking hy-drophilic chains, even in the absence of specific interactionsites.[17,18] Such hydrophobic effects are referred to as lateral hy-drophobic effects in this study. Appropriate substituents in thesheet-like structures assemble, inducing further ordered struc-tures (Figure 1a). More dynamic assembled states, includingsolvents, such as lyotropic liquid crystals (LLCs), are formedthrough the aggregation of amphiphilic molecules driven by hy-drophobic effects.[19] Among LLCs, lyotropic chromonic liquidcrystals (LCLCs), formed by 𝜋-electronic systems, such as dyesand nucleic acids, exhibit molecular stacking not only throughhydrophobic effects but also via 𝜋–𝜋 interactions,[20–22] as seenin thermally responsive nanostructures of amphiphilic perylenebisimides.[23–25] The ionic moieties of the mesogens and the cor-responding counterions located outside the columnar structuresenhance the affinity for water molecules.[26–32]Introducing charges into 𝜋-electronic core units generatescharged 𝜋-electronic systems and their corresponding ion-pairing assemblies.[33–39] In particular, alternately stacked 𝜋-electronic cations and anions form charge-by-charge assem-blies via i𝜋–i𝜋 interactions, mainly comprising electrostaticand dispersion forces (Figure 1b).[33] Charge-by-charge as-semblies are observed in various forms, such as crystalsand thermotropic liquid crystals, depending on the periph-eral substituents.[34–38] Among 𝜋-electronic cations, porphyrinSmall 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (1 of 11)http://www.small-journal.commailto:maedahir@ph.ritsumei.ac.jphttps://doi.org/10.1002/smll.202511729http://creativecommons.org/licenses/by/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fsmll.202511729&domain=pdf&date_stamp=2025-11-25www.advancedsciencenews.com www.small-journal.comFigure 1. a) Self-assembly, showing the formation of assembled structures depending on directional interaction sites, b) charge-by-charge assembliesvia i𝜋–i𝜋 interactions of 𝜋-electronic ion pairs, c) i) porphyrin AuIII complexes, represented as a parent structure, and ii) PCCp– as building units ofion-pairing assemblies, and d) porphyrin AuIII complexes with hydrophilic substituents forming amphiphilic ion-pairing assemblies depending on theperipheral substituents.Small 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (2 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 2. Synthesis of amphiphilic porphyrin AuIII complexes as ion pairs.AuIII complexes have provided various ion-pairing assembliesdepending on the substituents and coexisting counteranions(Figure 1c (i)).[34,36,38] An amphiphilic porphyrin AuIII com-plex that has hydrophilic aryl units at the four meso-positionsforms LCLCs in combination with pentacyanocylcopentadi-enide (PCCp–)[40,41] as a 𝜋-electronic anion via the synergis-tic use of i𝜋–i𝜋 interactions and hydrophobic effects betweencharged 𝜋-electronic systems (Figure 1c (ii)).[39] Throughoutthis report, such synergistic interactions will be termed am-phiphilic i𝜋–i𝜋 interactions. Charge-by-charge columnar struc-tures were unidirectionally oriented under a magnetic field,and single-stranded charge-by-charge assemblies, as buildingunits of LCLCs, were observed using transmission electronmicroscopy (TEM). The approach that uses amphiphilic i𝜋–i𝜋interactions is different from other strategies that include 𝜋–electronic systems bearing charged peripheral substituents.[26–30]However, in our previous study, only LCLCs composed of 1Dcolumnar assemblies were formed owing to nanoscale phase sep-aration between charge-by-charge columns and peripheral hy-drophilic aryl units. Multidirectionally controlled arrangementin LCLCs requires specific interaction sites that promote lateralpacking between the columns. Modifying the substitution posi-tions of hydrophilic aryl units in porphyrin AuIII complexes, to-gether with 𝜋-electronic anions, would facilitate the formation ofLCLCs based on sheet-like structures through proximal interac-tions at the unsubstituted sites (Figure 1d). This study shows themulti-directional arrangement of 𝜋-electronic ion pairs, provid-ing, to the best of our knowledge, the first example of lamello-columnar (Lamcol)-based LCLCs, via lateral hydrophobic effectsbetween amphiphilic charge-by-charge columnar structures.2. Results and Discussion2.1. Synthesis and Characterization of Amphiphilic 𝝅-ElectronicCationsHydrophilic substituents such as CH3(OCH2CH2)3O (triethy-lene glycol, TEG) moieties were introduced for hydrationto form assemblies in aqueous media. Amphiphilic por-phyrin AuIII complex 1au+ (Figure 2) was synthesized as aCl– ion pair by AuIII complexation of 5,15-bis(3,4,5-trisTEG-substituted aryl)porphyrin[42] 1 by treatment with KAuCl4·nH2Oand NaOAc·3H2O in AcOH. PCCp– was introduced to provide𝜋-electronic ion pair 1au+-PCCp– by ion-pair metathesis of 1au+-Cl– with NaPCCp (Figure 2). As a reference for the relative ra-tio between hydrophilic and hydrophobic parts, amphiphilic por-phyrin AuIII complex 2au+ with CH3(OCH2CH2)6O (hexaethy-lene glycol, HEG) chains instead of TEG chains was also synthe-sized as a PCCp– ion pair. The synthesized ion pairs were charac-terized using 1H and 13CNMR spectroscopy and ESI-TOF-MS. InCDCl3 (1 mm) at 20 °C, the 1H NMR signals of 𝛽-CH proximal toArTEG (9.67 ppm) and aryl-CH (7.69 ppm) of 1au+ in 1au+-PCCp–showed downfield shifts compared to those of 1au+-Cl– (9.56 and7.52 ppm, respectively) (Figures S4, S6, S8, and S9, SupportingInformation). In contrast, the signals of 𝛽-CH on the far sideto ArTEG (9.86 ppm) and meso-CH (11.07 ppm) of 1au+ in 1au+-PCCp– were shifted upfield compared to those of 1au+-Cl– (10.05and 11.47 ppm, respectively). These shifts could be attributed tothe location ofmeso-CH on the 𝜋-plane of PCCp– in the 𝜋-stackedion pair (𝜋-sip).In CH2Cl2 (≤0.10 mm), UV/vis absorption spectra of 1au+-Cl–and 1au+-PCCp– showed the maxima (𝜆max) of the Soret band at399 nm, suggesting that the ion pairs exist in dispersed stateswithout aggregation (Figure S16, Supporting Information).[43] Incontrast, in aqueous solutions (0.10 mm), 1au+-Cl– and 1au+-PCCp– exhibited blue-shifted absorptions with the 𝜆max at 390and 398 nm, respectively (Figure S16, Supporting Informa-tion). The difference in the blue shifts can be attributed tothe anion-dependent assembly modes. The separation with adistance of ≈0.7 nm in a charge-by-charge assembly of 1au+-PCCp– induced a smaller exciton coupling between 1au+ unitsand resulted in a slight blue shift (1 nm). Charge-by-charge as-sembly was formed via effective amphiphilic i𝜋–i𝜋 interactions(1au+ and PCCp–). In contrast, 1au+-Cl–, with the hydration ofCl–, formed a stacking arrangement of 1au+ as suggested bythe larger blue shift (9 nm). In aqueous solutions, these ionSmall 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (3 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.compairs constructed assembled structures with sizes of ≈500 nm,as indicated by DLS measurements (Figure S20, SupportingInformation).2.2. Thermotropic Liquid Crystals of Amphiphilic Ion PairsAccording to solution behavior, bulk-state ion-pairing assembledstructures were examined. In 1au+-PCCp–, a paste-state sampleprecipitated from CHCl3/n-hexane,[44] the transitions at 74 and151 °C (heating) and 151 and 65 °C (cooling) were observed viadifferential scanning calorimetry (DSC) (Figure 3a; Figure S26,Supporting Information). Polarized optical microscopy (POM)images showed mosaic textures at 20 and 150 °C upon coolingfrom the isotropic liquid (Iso) state (Figure 3b). Synchrotron X-ray diffraction (XRD) at 20 °C upon heating showed the diffrac-tion pattern derived from the Lamcol structure (Lamcol-L) with a= 3.14 nm, b = 0.99 nm, and c = 0.72 nm (Figure 3c (i)), and thatat 150 °C upon heating revealed the Lamcol structure (Lamcol-H)with a = 3.12 nm, b = 1.07 nm, and c = 0.67 nm (Figure 3c (ii)).The sharp diffraction peaks in these Lamcol structures would bederived from the ordered arrangement of 1au+ and PCCp–. Theobserved a values indicated constituent sizes that were consis-tent with the model structure of 1au+ with folded TEG chains(Figure S69, Supporting Information), whereas the b values wereattributed to the intercolumnar distance along the b axis resultingfrom the packing between the unsubstituted sites of 1au+. Thec values reflect an alternately stacked arrangement of ion pairs,which is typical of charge-by-charge assemblies. The formationof Lamcol phases depended on the substitution position of the hy-drophilic aryl units; an intercolumnar arrangement was observedalong the b axis. In contrast, the paste-state 1au+-Cl–, precipitatedfrom CHCl3/n-hexane, showed a complex synchrotron XRD pat-tern derived from the highly crystalline mesophase (Figure S70,Supporting Information),[45] suggesting that coexisting anions inthe ion pairs of 1au+ are essential for assembly.The shearing-induced alignment of the sample between thepolyimide films contributed to revealing the difference betweenthe two Lamcol structures (Lamcol-L and -H) through synchrotronXRD analysis (Figures S77 and S78, Supporting Information).The diffractions at 25 °C derived from the lamellar pattern inLamcol-L were augmented in the equatorial direction. In contrast,those derived from the ordered arrangement of columns in asheet structure and charge-by-charge assembly mode increasedin the shearing (meridional) direction. Upon heating at 150 °C,the Lamcol-H structure retained the shear-induced alignment, ex-hibiting the same orientation as the Lamcol-L structure at 25 °C.The alignment tendency suggests that the sheet-like structureswere oriented perpendicularly to the polyimide films by the shear-ing process, with contributions from two types of domains show-ing either the b or c axis parallel to the shearing direction (FigureS78, Supporting Information). In the shearing direction, spac-ings of 0.71 and 0.67 nm for the Lamcol-L structure at 25 °C andthe Lamcol-H structure at 150 °C, respectively, were observed,corresponding to the (001) faces of the alternately stacked ion-pairing structures. The values of 0.99 and 1.07 nm, which wereobserved in the shearing direction of the Lamcol-L structure at25 °C and the Lamcol-H structure at 150 °C, respectively, couldbe attributed to the (010) faces, the repeating intercolumnar dis-tance along the b axis (Figure S77, Supporting Information).[46,47]As indicated by the b and c values in the Lamcol-L structures,the proposed sheet structures were formed by slipped stackedcolumns without the tilted 1au+ core units (Figure 3c (i)). Incontrast, in the possible Lamcol-H structures, the sheet struc-tures were formedwith tilted 1au+ cores without slipped stacking(Figure 3c (ii)). This tilted arrangement could be suggested by thevalue of 0.96 nmobserved 25° away from the shearing direction at150 °C (Figure S77, Supporting Information).[48,49] Higher tem-peratures induced larger a values in the Lamcol-L structures be-cause of the spreading of the TEG chains along the a axis (FigureS72, Supporting Information). In contrast, in the Lamcol-H struc-tures, the spreading of the TEG chains within the b–c plane, at-tributed to the elongation of the lateral distance between the un-substituted sites of 1au+ with the tilted cores, resulted in smallera values.[50] This behavior revealed that thermotropic liquid crys-tals were formed based on highly ordered assemblies, ascribedto charge-by-charge stacking of 1au+ and PCCp– via amphiphilici𝜋–i𝜋 interactions and also to lateral hydrophobic effects at prox-imally located unsubstituted sites of 1au+.2.3. Lyotropic Chromonic Liquid Crystals of Amphiphilic Ion PairsThe assembly behavior of the water-containing states of 1au+-PCCp– was further examined. The water-containing 1au+-PCCp–, in the percentages (w/w) of ion pairs to the total amounts(ion-pair content) of 70–1%, were prepared from 1au+-PCCp–(1au+-PCCp–100%) and the corresponding amounts of water. ThePOM textures at r.t. were dependent on the ion-pair content(Figure 4a). The water-containing states with ion-pair contentof 70%, 60%, 50%, and 40%, 1au+-PCCp–70%/60%/50%/40% labeledwith the corresponding content, formed Lamcol structures at r.t.,as revealed by synchrotronXRD,whereas 1au+-PCCp–30% and thestates with higher water amounts showed no diffraction peaksderived from Lamcol-based structures (Figure 4b,c). The a valuesof 3.39, 3.44, 3.67, and 3.96 nm for 1au+-PCCp–70%/60%/50%/40%,respectively, were correlated with the extended inter-sheet dis-tances due to more effective hydration at the TEG chains. Inparticular, the diffraction patterns of 1au+-PCCp–50%/40% indi-cated lower crystallinity than those of 1au+-PCCp–100%/70%/60%,suggesting phase transitions to Lamcol phases by hydration ofthe TEG chains (Figure 4b,c). The (001) diffractions at 0.66, 0.66,0.66, and 0.65 nm for 1au+-PCCp–70%/60%/50%/40%, respectively,suggested the formation of charge-by-charge assemblies with-out slipped stacking in the presence of water.[51] Furthermore,in 1au+-PCCp–50%/40%, the broad (010) diffractions at 0.95 and0.98 nm, respectively, showed no tilted 1au+ core owing to theefficient hydration of a sheet structure. These observations in-dicated that 1au+-PCCp– in the Lamcol phases exhibited LCLCbehaviors based on 2D organized structures via the amphiphilici𝜋–i𝜋 interactions between 1au+ and PCCp– and the lateral hy-drophobic effects with a notable contribution from the unsub-stituted sites of 1au+. Increased amounts of water resulted ina less ordered arrangement of the lamellar structures, as seenin 1au+-PCCp–30%/20%, which formed nematic sheet (labelled asNsheet in this study) phases with only orientational ordering, assupported by the POM textures (Figure 4a,c; Figure S50, Sup-porting Information). The absence of diffraction or broadeningSmall 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (4 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 3. a) Phase transition behavior of 1au+-PCCp– with DSC profiles, b) POM images at i) 20 °C and ii) 150 °C upon cooling, and c) synchrotronXRD and possible assembled models at i) 20 °C and ii) 150 °C upon heating. The axis labels in c) correspond to the packing parameters.Small 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (5 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 4. a) POM images of i) 1au+-PCCp–50%, ii) 1au+-PCCp–30%, and iii) 1au+-PCCp–10% at 20 °C, b) synchrotron XRD of 1au+-PCCp– and water-containing 1au+-PCCp– at 25 °C, and c) phase changes according to the ion-pair content. Shaded bars show the highly ordered mesophases.Small 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (6 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 5. Diagram of phase changes of water-containing 1au+-PCCp– by thermal transitions. Shaded bars show the highly ordered mesophases.peaks at ≈1.0 nm, corresponding to the intercolumnar distance(b), suggested a reduced number of repetitions and decreased or-dering due to increased fluidity. 1au+-PCCp–10%/1% showed noPOM textures at r.t. owing to the isotropically dispersed sheetstructures, labeled as Isosheet, with charge-by-charge assembliesin non-LCLC states (Figure 4a,c; Figure S52, Supporting Infor-mation). The stacking diffractions (c) at 0.65 and 0.66 nm, respec-tively, were weak, suggesting the retention of charge-by-chargeassemblies.The thermal conditions and ion-pair content influenced the as-sembly modes in the LCLCs of 1au+-PCCp– (Figure 5).[52] For ex-ample, 1au+-PCCp–40% in a Lamcol phase at r.t. showed thermaltransitions at 45 and 77 °C upon heating, as revealed by DSC(Figure S29, Supporting Information). Synchrotron XRD at 25and 60 °C upon heating showed the formation of two Lamcolphases (Lamcol and Lamcol´phases) with a values of 3.96 and3.29 nm, b values of 0.98 and 1.09 nm, and c values of 0.65and 0.67 nm, respectively, whereas, at 40 °C, diffraction peaksfrom the sheet structure without Lamcol pattern (b = 0.97 nm,c = 0.65 nm) were observed (Figure S96, Supporting Informa-tion). The POM texture at 40 °C suggests the formation of a Nsheetphase within a small temperature range (Figure S48, Support-ing Information). At <45 °C, the inter-sheet distances and or-dering were mainly controlled by thermal motion. At 45 °C, theLamcol´structure was formed owing to deswelling by partial de-hydration upon heating. POM observation at 90 °C showed notextures, suggesting that partially hydrating TEG chains caused aphase transition to an Iso state at lower temperatures than 1au+-PCCp–100%.1au+-PCCp–30%/20% in the Nsheet phases at r.t. showed thermaltransitions like those of 1au+-PCCp–40%, as seen in the transi-tions at 49 and 76 °C for 1au+-PCCp–20% (Figures S29 and S50,Supporting Information). At 60 °C, inducing dehydration, 1au+-PCCp–20% showed another Lamcol phase (Lamcol´phase) with a,b, and c values of 3.24, 0.99, and 0.66 nm, respectively, as revealedby synchrotron XRD (Figure S102, Supporting Information).[53]Above 76 °C, the phase, being invisible under POM and show-ing no diffraction peaks, suggested a transition to an Iso state.The states with high water content, such as 1au+-PCCp–10% inan Isosheet phase at r.t., enhanced lateral hydrophobic effects, re-sulting in deswelling due to dehydration at <76 °C upon heating.1au+-PCCp–10% exhibited thermal transitions at 31, 50, and 75 °C,the first of which was indicated by POM (Figures S29 and S51,Supporting Information). At 40 °C, synchrotron XRD revealedthat 1au+-PCCp–10% exhibited a Nsheet phase upon dehydration,with a c value of 0.66 nm (Figure S104, Supporting Information).Furthermore, at 70 °C, 1au+-PCCp–10% showed a Lamcol´phaseupon dehydration, with a and c values of 3.09 and 0.66 nm,respectively, as revealed by synchrotron XRD. 1au+-PCCp–1%,showing no phase transition to a Nsheet phase, exhibited the phasetransition from the Isosheet phase at r.t. to the Lamcol´phase witha and c values of 3.25 and 0.65 nm, respectively, at 60 °C (FiguresS29, S52, and S106, Supporting Information). In the states with≤50% ion-pair content, dehydration induced enhanced orderingfrom 45 °C to the temperatures at which the phases were con-verted to Iso states. The observed thermal transitions to sheet-basedmesophases suggest a high organizing ability via lateral hy-drophobic effects between amphiphilic charge-by-charge-basedcolumns. In contrast, swelling by hydration upon cooling in-duced phase transitions to less-ordered phases. However, exceptfor 1au+-PCCp–10%/1%, which showed the difficulty in hydrationupon cooling, sheet structures of different sizes and orders wereformed in separated domains with different ion-pair content.Water-containing 1 (170%/50%/20%) exhibited no LCLCs, sug-gesting that ion pairing is necessary for the formationof ordered structures (Figures S27, S37–S39, and S79–S81,Supporting Information). Water-containing 1au+-Cl– (1au+-Cl–75%/70%/60%/50%/20%) showed the LCLC behaviors (Figures S28,S40–S44, and S82–S89, Supporting Information). However,1au+-Cl–, which has no efficiently stackable anions, exhibiteda high affinity for water molecules, resulting in difficulty incontrolling the structures of LCLCs. 1au+-Cl–75%/70% formed rect-Small 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (7 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comangular columnar (Colr) phases with a value of 5.57 and 5.58 nmand b values of 1.92 and 1.94 nm, respectively, at 25 °C. At≤60% ion-pair content, no ordered arrangements were observed.Thus, the synergistic amphiphilic i𝜋–i𝜋 interactions and lateralhydrophobic effects seen in 1au+-PCCp– with various ion-paircontent were found crucial for controlling the assembly modesof LCLCs. In particular, the unsubstituted parts of 1au+ alignedby charge-by-charge assembly cooperatively interact via lateralhydrophobic effects to form sheet-like structures and resultingLamcol phases. Synergistic amphiphilic i𝜋–i𝜋 interactions and lat-eral hydrophobic effects are essential to induce ordered arrange-ments in multiple directions.2au+-PCCp–, bearing HEG chains as longer hydrophilic sidechains, provided different LCLC structures. In the absence ofwater, the elongation of the side chains led to reduced colum-nar alignment, resulting in charge-by-charge-based columns (c =0.68 nm) that were isotropically dispersed (Isocol) without form-ing organized structures (Figures S26, S36, S76, and S128, Sup-porting Information). On the other hand, water-containing 2au+-PCCp–70%/60%/50%/40% formed hexagonal columnar (Colh) struc-tures (Z = 1 for 𝜌 = 0.88) with a and c values of 2.90 and 0.68 nm,respectively, for 2au+-PCCp–70%, as an example, via amphiphilici𝜋–i𝜋 interactions (Figures S32, S60–S63, and S115–S122, Sup-porting Information). In these Colh structures, HEG chainsfolded around the unsubstituted regions, thereby inhibiting theirlateral hydrophobic effects to form sheet-like structures. Further-more, 2au+-PCCp–30% and the states with higher water contentshowed the formation of sheet structures and resulting Lamcolphases via lateral hydrophobic effects at the unsubstituted sites(Figures S32, S64–S67, and S123–S128, Supporting Informa-tion). At ≤70% ion-pair content, thermal motion mainly con-trolled the inter-sheet and intercolumnar distances and order-ing below the partially dehydrated transition temperatures (61–82 °C). Above these temperatures, the partial dehydration in-duced deswelling, leading to Isocol´states.[54] For example, 2au+-PCCp–30% in a Lamcol phase (a = 4.07 nm, c = 0.67 nm) at r.t.showed thermal motions, forming the Nsheet phase at 50 °C uponheating (Figures S32, S64, and S123, Supporting Information).At 60 °C, the Isocol´phase was formed due to deswelling by par-tial dehydration upon heating. Upon cooling to 50 °C, the sheetstructures were hydrated, forming a Lamcol phase. Furthermore,at 30 °C, synchrotron XRD of 2au+-PCCp–30% suggested the for-mation of dimers proximally located at the unsubstituted sitesvia the partial dissociation of intercolumnar arrangements alongthe b axis driven by lateral hydrophobic effects, providing a Colhphase. Tuning the relative ratio of hydrophilic to hydrophobicparts and the amount of water enabled control over the associ-ations and dissociations in the hydrophobic regions, resulting inthe formation of various assembled structures based on charge-by-charge stacking.2.4. Macroscopically Oriented Structures in Magnetic FieldsThe anisotropic magnetic susceptibility of 1au+-PCCp–, alongwith the viscosity tunability via MeOH content control,[55]would be used to induce macroscopically oriented assembledstructures.[39,56–59] The sample of the ion pair in MeOH exhib-ited superior alignment compared to that in aqueous solutions.The Lamcol structure fabricated under the slow condensation of1au+-PCCp–10% in MeOH drop-cast on a glass substrate by va-porizing MeOH for 14 h showed no orientation of Lamcol do-mains (Figure 6a; Figure S130a, Supporting Information). Incontrast, 1au+-PCCp–10% in MeOH in a 10-T magnetic field ap-plied along the glass substrate was initially less viscous and re-sponsive to the magnetic field, followed by conversion to a vis-cous state that maintained the oriented structure even withoutthe magnetic field after the drying procedure. The brightnessof the POM for the dried sample changed homogeneously anddrastically depending on the angular geometry, indicating thatthe charge-by-charge-based sheet-like structures were orientedin one direction along the glass substrate (Figure S130b, Sup-porting Information).[56] 2D XRD revealed anisotropic (001) and(002) diffractions derived from charge-by-charge assemblies inthe equatorial region (Figure 6b). In contrast, diffractions from alamellar pattern with (100) and (200) diffractions were observedin the meridional region. These observations suggest that thesheet-like structures comprising charge-by-charge columns wereoriented with the layer normal that was parallel to the magneticfield.[59] Furthermore, the 2D XRD showed no (010) diffraction,suggesting a lamellar structure perpendicular to the glass sub-strate and excluding the possibility of sheet-like structures paral-lel to the substrate.A magnetic field rotating in-plane with respect to the glasssubstrate induces a vertical orientation of the columns in asheet-like structure.[58] The same condensation process per-formed under a 10-T magnetic field with the glass substraterotated in-plane at 20 rpm resulted in the orientation ofthe columns perpendicular to the rotation plane. The POMobservations of the resulting sample exhibited slight angle-independent birefringence, as seen in the vertically orientedcolumns and resulting Lamcol structures (Figure S130c, Support-ing Information).[57] In addition, the resulting sample showedalmost no (001) and (002) diffractions derived from charge-by-charge assemblies, further supporting the vertical orientation ofthe columns (Figure 6c). In contrast, the (010) diffraction wasthe highest, suggesting strong lateral hydrophobic effects evenunder dynamic conditions with magnetic field-induced align-ment control. The weak (100) diffraction showed smaller do-mains caused by the disruption of the lamellar pattern undera magnetic field rotating within the plane of the glass sub-strate. The charge-by-charge-based sheet-like structure of 1au+-PCCp– can be macroscopically oriented in a single direction ondemand.2.5. STEM Observations of Charge-by-Charge-Based Sheet-LikeStructuresAmphiphilic i𝜋–i𝜋 interactions and lateral hydrophobic effectsbetween columnswould effectively contribute to the organizationeven in a dilute aqueous solution. Charge-by-charge-basedmono-layer sheet-like structures were observed by bright-field scanningtransmission electron microscopy (BF-STEM) in a non-stainedspecimen prepared from a dilute aqueous solution of 1au+-PCCp– (25 μm) upon the deposition on a thin carbon film viafreeze-drying processes (Figure 7a). This result suggests that theinteractions between the sheet-like structures at the hydrophilicSmall 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (8 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 6. 2D XRD images of the samples of 1au+-PCCp– cast on glass substrates, which were prepared by slow vaporization of MeOH from 1au+-PCCp–10%: a) without a magnetic field, b) with a 10-T static magnetic field applied along the glass substrate, and c) with a 10-T magnetic field rotatingin-plane of the glass substrate.substituent regions are weak compared to the amphiphilici𝜋–i𝜋 interactions and lateral hydrophobic effects, and charge-by-charge assemblies are crucial for ordered structures. The homo-geneous contrast suggests that the sheet-like structures have auniform thickness. The high image contrast in the correspond-ing high-angle annular dark-field STEM (HAADF-STEM) im-age suggests the presence of heavy Au atoms in the sheet-likestructures (Figure 7b). This observation was consistent with theSTEM energy-dispersive X-ray spectroscopy (EDS) images ob-tained (Figure S131, Supporting Information). AFM observationof an aqueous solution of 1au+-PCCp– (25 μm) on a Si wafer viafreeze-drying processes showed the uniform thickness of 2.9–4.0 nm, indicating themonolayer sheet-like structures (Figure 7c;Figure S132, Supporting Information). The direct observation ofcharge-by-charge-basedmonolayer sheet-like structures suggeststhat the synergistic use of amphiphilic i𝜋–i𝜋 interactions and lat-eral hydrophobic effects is essential for producing multidirec-tionally organized structures.3. ConclusionIon pairs of amphiphilic porphyrin AuIII complexes bearing hy-drophilic aryl units at the 5,15-positions were synthesized fordimension-controlled assembly. In the PCCp– ion pair of theTEG-substituted cation, synchrotron XRD revealed the forma-tion of thermotropic liquid crystals comprising sheet-like struc-tures arranged in a charge-by-charge assembly via amphiphilici𝜋–i𝜋 interactions. The proximal locations at the unsubstitutedsites of the porphyrin AuIII complex contributed to the forma-tion of Lamcol phases, whichwere characterized by highly orderedarrangements. In the water-containing states, charge-by-charge-based Lamcol, Nsheet, and Isosheet phases were constructed depend-ing on the water amount and temperature, exhibiting LCLC be-haviors for the first two phases. Unlike in crystalline solids, theordering along the directions via amphiphilic i𝜋–i𝜋 interactions,lateral hydrophobic effects, and hydrophilic interactions are notmutually correlated in the studied LCLCs. Furthermore, thecharge-by-charge-based sheet-like structure in the Lamcol phasewas unidirectionally oriented after drying under amagnetic field.Charge-by-charge-based monolayer sheet-like structures wereobserved as the components of LCLCs using STEM and AFMfrom a diluted aqueous solution via freeze-drying. These observa-tions suggest that amphiphilic charged 𝜋-electronic systemsweremultidirectionally organized via amphiphilic i𝜋–i𝜋 interactionsand lateral hydrophobic effects between the charge-by-charge-based columns. The relative ratio of hydrophilic and hydropho-bic regions is essential for constructing 2D organized structures.Ion-pairing-based organization without substituents involved indirectional interactions can facilitate the control of assemblymodes and properties by introducing hydrophobic substituentsand other counterions. Charge-by-charge columnar assembliesand their proximal locations would provide 2D anisotropic func-Small 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (9 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.comwww.advancedsciencenews.com www.small-journal.comFigure 7. a) BF-STEM, b) HAADF-STEM, and c) AFM images of 1au+-PCCp– as monolayer sheet-like structures formed in aqueous solutions (25 μm).tional materials, some of which may exhibit stimuli-responsiveferroelectric properties derived from 𝜋-sip-based supramoleculardipoles.Supporting InformationSupporting Information is available from the Wiley Online Library or fromthe author.AcknowledgementsThis work was supported by JSPS KAKENHI Grant Numbers JP18H01968,JP22H02067, and JP23K23335 for Scientific Research (B), JP23K17951 forChallenging Research (Exploratory), JP20H05863 for Transformative Re-search Areas (A) “Condensed Conjugation”, JP23H04874 for Transfor-mative Research Areas (A) “Materials Science of Meso-Hierarchy”, Rit-sumeikan Global Innovation Research Organization (R-GIRO) project(2017–22 and 2022–27), and JST SPRING Grant Number JPMJSP2101.Theoretical calculations were partially performed using the Research Cen-ter for Computational Science, Okazaki, Japan (Projects: 21-IMS-C077, 22-IMS-C077, 23-IMS-C069, 24-IMS-C067, and 25-IMS-C069). Synchrotron-radiation analysis was performed at BL19B2 (2024B1925, 2024B2119,2025A1560, 2025A1760, and 2025A1951) and BL40B2 (2024A1463 and2025A1607) of SPring-8 with the approval of the Japan Synchrotron Ra-diation Research Institute (JASRI). The authors thank Dr. Noboru Ohtaand Dr. Shigeo Kuwamoto, JASRI/SPring-8, for synchrotron XRDmeasure-ments, Dr. Hiroki Tanaka and Mr. Keita Ono, Ritsumeikan University, forthe synthesis of NaPCCp, and Prof. Hitoshi Tamiaki, Ritsumeikan Univer-sity, for various measurements.Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are available in the sup-plementary material of this article.Keywordsamphiphilic i𝜋–i𝜋 interactions, charged 𝜋-electronic systems, ion-pairingassemblies, lateral hydrophobic effects, multi-directional organizationReceived: September 24, 2025Revised: November 14, 2025Published online: November 25, 2025[1] T. S. Kale, A. Klaikherd, B. 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Caricato, A. V. Marenich, J. Bloino, B. G. Janesko,R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov,J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi,J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, et al.,Gaussian 16, Revision C.01, Gaussian Inc, Wallingford CT, USA, 2016.[44] The paste-state sample showed a highly ordered mesophase basedon a lamellar structure as indicated by synchrotron XRD.[45] 1au+-Cl– showed no phase transitions by DSC, whereas synchrotronXRD and POM observation suggested phase transition to the Isostate at 170 and 140 °C, respectively (Figures S26, S33, and S70, Sup-porting Information).[46] A. Akbari, P. Sheath, S. T. Martin, D. B. Shinde, M. Shaibani, P. C.Banerjee, R. Tkacz, D. Bhattacharyya, M. Majumder, Nat. Commun.2016, 7, 10891.[47] X. Feng, W. Pisula, L. Zhi, M. Takase, K. Müllen, Angew. Chem., Int.Ed. 2008, 47, 1703.[48] A. Mori, M. Yokoo, M. Hashimoto, S. Ujiie, S. Diele, U. Baumeister,C. 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Sci. 1996, 21, 775.[53] In the Nsheet phases of 1au+-PCCp–30%/20% upon heating, diffrac-tion peaks corresponding to distances of ≥5.32 nm, exceeding themolecular length, were observed due to the less ordered inter-sheetdistances (Figures S100 and S102, Supporting Information). The de-tails will be discussed elsewhere.[54] Synchrotron XRD of 2au+-PCCp–70%/60%/50%/40% upon cooling fromthe Isocol´phases suggested that domains with different concentra-tions were obtained by incomplete hydration.[55] The use of MeOH, which tunes the viscosity without disrupting thecharge-by-charge stacking and lateral hydrophobic packing, insteadof water showed no significant influence on the formation of the Lam-col structures during slow drying process.[56] M. Yoshio, T. Kagata, K. Hoshino, T. Mukai, H. Ohno, T. Kato, J. Am.Chem. Soc. 2006, 128, 5570.[57] G. Schweicher, G. Gbabode, F. Quist, O. Debever, N. Dumont, S.Sergeyev, Y. H. Geerts, Chem. Mater. 2009, 21, 5867.[58] X. Feng, M. E. Tousley, M. G. Cowan, B. R. Wiesenauer, S. Nejati, Y.Choo, R. D. Noble, M. Elimelech, D. L. Gin, C. O. Osuji, ACS Nano2014, 8, 11977.[59] C. Li, J. Cho, K. Yamada, D.Hashizume, F. Araoka, H. Takezoe, T. Aida,Y. Ishida, Nat. Commun. 2015, 6, 8418.Small 2026, 22, e11729 © 2025 The Author(s). Small published by Wiley-VCH GmbHe11729 (11 of 11) 16136829, 2026, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202511729 by National Institute For, Wiley Online Library on [14/01/2026]. 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.small-journal.com Multidirectionally Controlled Arrangement via Ion-Pairing Assembly of Amphiphilic Charged 83À-Electronic Systems 1. Introduction 2. Results and Discussion 2.1. Synthesis and Characterization of Amphiphilic 83À-Electronic Cations 2.2. Thermotropic Liquid Crystals of Amphiphilic Ion Pairs 2.3. Lyotropic Chromonic Liquid Crystals of Amphiphilic Ion Pairs 2.4. Macroscopically Oriented Structures in Magnetic Fields 2.5. STEM Observations of Charge-by-Charge-Based Sheet-Like Structures 3. Conclusion Supporting Information Acknowledgements Conflict of Interest Data Availability Statement Keywords