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Zhehui Jin, [Masayuki Takeuchi](https://orcid.org/0000-0002-0207-0665), [Yutaka Wakayama](https://orcid.org/0000-0002-0801-8884), [Kazunori Sugiyasu](https://orcid.org/0000-0001-5699-2772)

## Rights

 This is the peer reviewed version of the following article: Jin, Z., Takeuchi, M., Wakayama, Y. and Sugiyasu, K. (2025), Polymerization Order in the Synthesis of 2D Block Supramolecular Copolymers. Chem. Eur. J., 31: e01739, which has been published in final form at https://doi.org/10.1002/chem.202501739. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

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[Polymerization Order in the Synthesis of 2D Block Supramolecular Copolymers](https://mdr.nims.go.jp/datasets/e911a77a-4b8e-4757-ab8f-021ecd5a80b9)

## Fulltext

JinZhehui 1 Polymerization Order in the Synthesis of Two-Dimensional Block Supramolecular Copolymers    Zhehui Jin,[a,b] Masayuki Takeuchi,[b] Yutaka Wakayama,[a,b] and Kazunori Sugiyasu*[c]  [a] Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan  [b] National Institute for Materials Science, Tsukuba, Ibaraki 305-0047, Japan  [c] Department of Polymer Chemistry, Kyoto University, Kyotodaigaku-katsura, Nishikyo-ku, Kyoto 615-8510, Japan    Abstract: In the synthesis of block polymers through living polymerization, the order in which the monomers are copolymerized can have a critical effect on the polymerization efficacy. The same should hold true for the synthesis of block supramolecular polymers; however, this remains unexplored. We investigated the effect of the order of the polymerization of the monomers in two-dimensional seeded/living supramolecular block copolymerization of porphyrin-based monomers. Unlike one-dimensional living polymers, two-dimensional supramolecular polymers (or nanosheets) have two distinct propagation sites. We showed that inverting the order of polymerization can lead to distinct growth modes; importantly, secondary nucleation is involved in one of these cases. If secondary nucleation takes place at the edges of the seeds prior to two-dimensional growth, the resulting nanosheets tend to exhibit uncontrolled areas and edge roughness.    ! #!*+$%,-.'$/,+)S(,@%9#5&R-&E%H%(;&@8E-4#9%7+2%8(!(%&+(5&E%H%(;&09-,2+EE%7+2%8(J59%H#(&,#EAJ+,,#4RE-&]B?:_^)!)#*%&E%H%(;&,$@9+48E#0$E+9& @8E-4#9%7+2%8(& ]`:V^& "+,& ,##(& ,%;(%A%0+(2& @98;9#,,& %(& 2"#& E+,2& 5#0+5#Y!+,-%&B8(,#a$#(2E-)& ,$@9+48E#0$E+9& @8E-4#9,& X%2"& (+998X& ,%7#& 5%,29%R$2%8(,!.%& +(5& RE80.& ,29$02$9#,!/#0%&"+H#&R#084#&+H+%E+RE#Y&K$92"#9489#)&R-&$,%(;&+@@98@9%+2#E-&5#,%;(#5&48(84#9,)&2X8J5%4#(,%8(+E&]b?^&,$@9+48E#0$E+9&@8E-4#9,&X%2"&08(298EE#5&+9#+,&"+H#&R##(&8R2+%(#5Y!1#-%&_,&%EE$,29+2#5&R-&E%H%(;&B?:_)!(2%& b?& ,29$02$9#,& +9#& 489#& +229+02%H#& 2"+(& M?& ,29$02$9#,& R#0+$,#& 8A& 2"#%9& 9%0"& H+9%#2-& 8A&,29$02$9+E&482%A,)&+(5&2"#%9&@9#0%,#&,-(2"#,#,&08$E5&E#+5&28&(#X&A$(02%8(+E&4+2#9%+E,Y&S(&2"%,&,2$5-)&X#&%(H#,2%;+2#5&b?&`:V&28&@985$0#&RE80.&,$@9+48E#0$E+9&(+(8,"##2,Y&S2&%,&X#EE&.(8X(&2"+2&28&8R2+%(&+&08@8E-4#9&X%2"&+&@+92%0$E+9&5#,%9#5&RE80.&,29$02$9#)&2"#&895#9&%(&X"%0"&2"#&48(84#9,&+9#&@8E-4#9%7#5&(##5,&28&R#&08(,%5#9#5&0+9#A$EE-Y!((%&K89&%(,2+(0#)&28&@985$0#&@8E-,2-9#(#J!"#$%J@8E-#2"-E#(#&8[%5#&]V:J!JVFc^&R-&E%H%(;&+(%8(%0&@8E-4#9%7+2%8()&2"#&V:&RE80.&"+,&28&R#&,-(2"#,%7#5&R#A89#&2"#&VFc&RE80.&]:0"#4#&M^Y!(("%&SA&2"#&,-(2"#,%,&%,&+22#4@2#5&%(&2"#&8@@8,%2#&895#9)&2"#&VFc&RE80.&X%2"&+(&+(%8(%0&0"+%(&2#94%($,&0+((82&#AA%0%#(2E-&%(%2%+2#&2"#&@8E-4#9%7+2%8(&8A&,2-9#(#& +,& +& 9#,$E2& 8A& %2,& E8X#9& 9#+02%H%2-Y& G(5#9,2+(5%(;& 8A& ,$0"& d@8E-4#9%7+2%8(& 895#9e& "+,&08(29%R$2#5&28&2"#&5#H#E8@4#(2&8A&@9#0%,%8(&,-(2"#,%,&8A&08H+E#(2&RE80.&@8E-4#9,&+(5&82"#9&@8E-4#9,&X%2"& $(%a$#& 28@8E8;%#,Z!()%& "8X#H#9)& 2"#& #AA#02& 8A& 2"#& @8E-4#9%7+2%8(& 895#9& "+,& ,0+90#E-& R##(&%(H#,2%;+2#5& A89& ,$@9+48E#0$E+9& 08$(2#9@+92,Y& c;%& +(5& 1+4+;$0"%& 9#0#(2E-& 9#@892#5& 2"#& 8(#J5%4#(,%8(+E& ]M?^& ,##5#5&`:V& 8A& 2"9##& 5%,2%(02& +4%(8& +0%5JR+,#5&48(84#9,Y!(*%& /"#-& A8$(5& 2"+2)&5#@#(5%(;&8(&2"#&084R%(+2%8(&8A&,##5&+(5&48(84#9&$,#5)&#%2"#9&08@8E-4#9%7+2%8(&89&,#EAJ,892%(;&800$99#5)&2"#9#R-&9#,$E2%(;&%(&5%AA#9#(2&@985$02,Y&/"#&4+%(&5#2#94%(+(2&8A&2"#&@8E-4#9%7+2%8(&895#9&X+,&,2#9%0&"%(59+(0#&R-&2"#&,%5#&9#,%5$#,&8A&2"#&+4%(8&+0%5,Y&S(&2"%,&08(2#[2)&+E2"8$;"&,#H#9+E&9#,#+90"&;98$@,)!-%&%(0E$5%(;&8$9,#EH#,)!1%&"+H#&9#@892#5&b?&`:V,)&2"#&,-(2"#,%,&8A&b?&RE80.&,$@9+48E#0$E+9&@8E-4#9,&9#4+%(,&0"+EE#(;%(;)!13%&+(5&2"#&#AA#02&8A&2"#&895#9&8A&@8E-4#9%7+2%8(&%(&2X8&5%4#(,%8(,&"+,&-#2&28&R#&%(H#,2%;+2#5Y&&&&&0'1232) 45& V8E-4#9%7+2%8(& 895#9& %(& 2"#& ,-(2"#,%,& 8A& @8E-,2-9#(#J!"#$%J@8E-#2"-E#(#& 8[%5#& ]V:J!JVFc^&H%+&E%H%(;&+(%8(%0&@8E-4#9%7+2%8(Y&ORRmO HnR OnORmOi)ii) H2O 3 Our 2D LSP has been established by using several porphyrin-based monomers (Scheme 2a). In terms of their mechanism, LSP has parallels with living CDSA, in that both methods rely on nucleation and growth processes and can be initiated by the external addition of seeds.[2-4] For example, in the 2D LSP of monomer 61,[8a] spontaneous nucleation is kinetically prevented by a coupled equilibrium that temporarily forms the metastable nanoparticles (NP-61). Addition of a separately prepared thermodynamically stable 2D seed (Seed-61) to a solution of NP-61 initiates 2D supramolecular polymerization to produce supramolecular nanosheets (NS-61) with a controlled area (Scheme 2b). The 2D growth is driven by hydrogen bonding of the amide groups and π-stacking of the porphyrin core in one axis (i.e., the x-axis) and by van der Waals interaction between the side chains (R groups) in another axis (the y-axis). In other words, 2D seeded growth involves two distinct propagation sites, an interesting characteristic not seen in 1D LSP. With these previous discoveries in mind, we investigated the effect of the order of polymerization of monomers in the synthesis of 2D block supramolecular copolymers.     4   Scheme 2. (a) Structures of our porphyrin-based monomers. (b) 2D living supramolecular polymerization of 61 (or 62, 63, 71, 6N3). In the nanosheets, porphyrin molecules are assembled through hydrogen bonding of the amide groups and π-stacking of the porphyrin core along the x-axis and by van der Waals interaction between the side chains (R groups) along the y-axis.   5 Results and Discussion Of the porphyrin derivatives investigated in our previous studies,[8] monomers 62, 63, and 6N3 were found to form stable 2D nanosheets (Scheme 2). We attributed the stability of these nanosheets in comparison with those of other porphyrin-based monomers such as 61 and 71 to an entropy factor that originates from the lower degree of conformational freedom of the unsaturated bonds in 62, 63, and 6N3.[8b] In this study, we mainly used monomers 63 and 6N3 to investigate block supramolecular copolymerization in two dimensions. Octadecyl chains are introduced to the gallic acid-based wedges so that agglomeration of nanosheets can be prevented (Scheme 2a).[8f] Methyl cyclohexane (MCH) was used as a solvent. First, we prepared 2D seeds consisting of 6N3 or 63 by our previously established procedure [see the Supporting Information (SI)];[8] hereafter, these 2D seeds are referred to as Seed-6N3 and Seed-63, respectively (Figures 1a). Number-average and weight-average areas (An and Aw, respectively) and the area distribution (Aw/An) were determined by atomic force microscopy (AFM) in conjunction with Image J software (SI, Figure S3). Reflecting a difference in the driving forces along the x- and y-axes (Scheme 2b), Seed-6N3 and Seed-63 have distinct aspect ratios of 1.60 and 2.86, respectively. This result suggested that 6N3 has a stronger propensity to self-assemble two dimensionally than 63. The split Soret bands (l = 380–460 nm) of Seed-6N3 and Seed-63 indicated that the porphyrin molecules in the nanosheets are stacked in short slipping J-aggregates (Figure 1b), a porphyrin stacking mode with a medium offset between those of the J- and H-aggregates.[8,14] Importantly, a small but significant difference in the absorption maxima between NS-6N3 (l = 444 nm) and NS-63 (l = 442 nm) was observed (Figure 1b, inset), suggesting that these two monomers pack in slightly different structures. We assumed that this would affect the polymerization order in a subsequent seeded heteropolymerization (i.e., block copolymerization).      6  Figure 1. (a) AFM images of Seed-6N3 and Seed-63 (bar = 500 nm): the preparations of these seeds are described in the SI. (b) Absorption spectra of Seed-6N3 (orange), Seed-63 (sky blue), NP-6N3 (dashed pink), and NP-63 (dashed blue): [Porphyrins] = 50 µM.   (a) Seed-6N3 Seed-63444 nm442 nm350 450 550 650Wavelength (nm)Absorbance00.51.01.52.0(b)10 7  Figure 2. (a) Absorption spectral changes observed during seeded polymerization: the case conducted using Seed-6N3 and NP-6N3 are displayed: [Seed-6N3] = [NP-6N3] = 25 µM in MCH, with respect to the concentration of 6N3. Note that the Soret band cannot be probed during this process because of the high molar-absorption coefficient. (Inset) Changes in the absorbance at 550 nm as a function of time. Spectral changes of other seeded growth are shown in the SI (Figures S4). (b) Kinetics of seeded/living 2D LSP, observed as changes in the absorbance at 550 nm during homo- and hetero-seeded polymerizations. (c) Values of t50 for the seeded growth process, determined from (b). (d) AFM images of NS-(6N3-6N3), NS-(63-63), NS-(6N3-b-63), and NS-(63-b-6N3) (bar = 500 nm). (e) Illustration of the calculation of the solidity (S), (f) histograms of area, (g) Aw/An values, (h) histograms of solidity, and (i) s/Sn values for the obtained nanosheets. Colours in Figures b, f, h correspond to those defined in Figures c, g, i, respectively. Solidity =AreaAreaNS-(6N3-6N3) NS-(63-63) NS-(6N3-b-63)(d) (e)HomoHeteroHomoHeteroNS-(6N 3-6N3)NS-(63-6 3)NS-(6N 3-b-6 3)NS-(63-b-6N3)NS-(6N 3-6N3)NS-(63-6 3)NS-(6N 3-b-6 3)NS-(63-b-6N3)104 105Area (nm2)020406010080Cummulative number1.0Solidity0.90.80.7Aw/Anσ /Sn1.01.11.21.31.41.500.010.020.040.060.070.030.05(g) (i)(f) (h)NS-(63-b-6N3) NS-(63-b-6N3)HomoHeteroNS-(6N 3-6N3)NS-(63-6 3)NS-(6N 3-b-6 3)NS-(63-b-6N3)t 50 (min)0103020(c)60Time (min)5040200 10 30Normalized Δabsorbance00.20.40.60.81.0(b)NS-(63-b-6N3)510 570 630Wavelength (nm)Absorbance00.40.81.6Absorbance at 550 nmTime (min)0 10 20 300.91.11.01.3(a)540 600Seed-6N3+ NP-6N3t50020406010080Cummulative number1.21.2103the same as the orange plot in (b)NS-(63-b-6N3) 8 Before investigating seeded heteropolymerization, seeded homopolymerization was conducted by mixing Seed-6N3 or Seed-63 with metastable nanoparticles consisting of the corresponding monomers NP-6N3 and NP-63. The seeded growth process was monitored by examination of the changes in the absorbance as a function of time (Figure 2a and SI, Figure S4), confirming the consumption of the metastable nanoparticles (i.e., J-aggregates) and the growth of the nanosheets (short-slipping J-aggregates). Note that during this time frame (~ 60 min), self-nucleation from the metastable nanoparticles does not occur.  As a result of this seeded growth process, we obtained supramolecular nanosheets with a controlled area and with relatively narrow Aw/An ratios (Figure 2d,f,g): these nanosheets are referred to as NS-(6N3-6N3) and NS-(63-63), respectively. Next, we performed seeded heteropolymerization to produce 2D diblock supramolecular copolymers. Unlike covalent block copolymerization (see Scheme 1), in the 2D seeded heteropolymerization, the first block is surrounded by the second block. Accordingly, the polymerization orders of 6N3-to-63 and 63-to-6N3 result in distinct 6N3⊂63 and 63⊂6N3 diblock structures, respectively: these are referred to as NS-(6N3-b-63) and NS-(63-b-6N3), respectively. Intriguingly, the shapes of NS-(6N3-b-63) and NS-(63-b-6N3) showed obvious difference (Figure 2d). We therefore used the solidity to evaluate the structures of the resulting nanosheets. In brief, solidity as defined by the equation shown in Figure 2e, quantifies the roughness of a shape, and its value approaches unity when the edge of the nanosheets is smooth.[8f] The histogram of solidity for the obtained nanosheets are shown in Figure 2h, indicating that the values of NS-(63-b-6N3) are broadly distributed in comparison with those of other nanosheets. Because each nanosheet can have distinct number-average solidity (Sn) depending on the structures of the monomer used,[8f] we compared the dispersion of the distribution of solidity based on the coefficient of variation (CV): i.e., s/Sn, where s is the standard deviation.[8c] Note that the value of s/Sn for NS-(63-b-6N3) was noticeably larger than those for the other nanosheets (Figure 2i). Moreover, the value of Aw/An for NS-(63-b-6N3) was also larger than those for the other nanosheets (Figures 2f,g). These results indicate that seeded growth of NS-(63-b-6N3) was not as well controlled as in the opposite case to produce NS-(6N3-b-63), suggesting that the order of polymerization is indeed important in 2D block supramolecular polymerization.  It is noteworthy that the kinetics of the seeded growth of NS-(63-b-6N3) followed a sigmoidal curve, whereas the other copolymers showed concave profiles (Figure 2b). In addition, the half-time (t50), defined as the time required for the consumption of 50% of the monomers (or, metastable nanoparticles, in this study), was significantly extended in this particular case (Figure 2c, the red bar). These results imply that secondary nucleation plays a pivotal role in the formation of NS-(63-b-6N3).[15-17] In fact, like other supramolecular polymerizations involving secondary nucleation, the seeded growth kinetics of NS-(63-b-6N3) showed a stronger concentration dependence in comparison with the other cases (SI; Figure S5d). Taking the above observations into account, we propose that the 2D seeded heteropolymerization proceeds by the plausible mechanism shown in Scheme 3. In relation to this mechanism, we have to consider several determinants of the polymerization order observed in this study. First, the molecular packing structures of 6N3 and 63 within nanosheets are slightly different, as suggested by the difference in the absorption maxima of the Soret band (Figure 1b). Secondly, the 6N3 molecule is  9 slightly larger than 63; therefore, epitaxial growth of 6N3 from Seed-63 is likely to be partially hindered. Thirdly, in the direction of the y-axis, the azide groups in 6N3 should additionally enhance the van der Waals force due to their 1,3-dipole, as evidenced by the smaller aspect ratio of Seed-6N3 (see above); therefore, 6N3 (or Seed-6N3) could be regarded to be more “reactive” than 63 (or Seed-63). A complex interplay of these determinants appears to cause the lattice mismatch during the block extension and increase the contribution of secondary nucleation of 6N3 at the edge of Seed-63 (Scheme 3). This secondary nucleation occurs slowly and sporadically; but once it occurs, the growth of NS-6N3 is initiated from that point (i.e., the secondary nuclei), which, in turn, leads to the formation of roughened edges. Because of the slow seeded growth kinetics, secondary nucleation would occur also at the surface of the nanosheets; we indeed observe smaller nanosheets piling up above some of the NS-(63-b-6N3) (Figure 2d). To verify the above mechanism, we investigated the formation of NS-62, which showed an absorption maximum at 442 nm, a value similar to that of NS-63 (SI; Figure S4). Like the case of 6N3 and 63 displayed in Figure 2, NS-(6N3-b-62) was obtainable, whereas NS-(62-b-6N3) had roughened edges. In addition, both orders of polymerization that produce NS-(62-b-63) and NS-(63-b-62) worked well, as evidenced by the lower values of Aw/An and s/Sn and by the shorter t50 (SI; Figure S6). Hence, a subtle difference between 6N3 and 63 (and 62) dictates the appropriate polymerization order in our 2D LSP (SI; Figure S6).   Scheme 3. Plausible mechanism for the observed polymerization order in the synthesis of 2D block supramolecular copolymers using 6N3 and 63.  10 Although nanosheets with larger s/Sn values, such as NS-(63-b-6N3), might be regarded as structurally ill-defined, their roughened edges are not necessarily a drawback when designing functional materials that require large circumferences (or roughened edges).[18] We expect that the ability to control the edge roughness of nanosheets by altering the order of polymerization might be useful for this purpose. As a proof of concept, we used metastable nanoparticles consisting of a mixture of 6N3 and 63 in various ratios: a = [6N3/(6N3+63)]×100 = 10–90%. Mixing such metastable nanoparticles with Seed-6N3 should produces NS-[6N3-b-(6N3+63)]-a. The sequence of the monomers in the second block can be either random or blocky,[6] the characterization of which is beyond the scope of the present study. The comparative AFM images of the resulting nanosheets are shown in Figure 3a: the values of Aw/An, and s/Sn remained similar on changing the ratio of 63 to 6N3 (Figures 3c and 3d). We also confirmed that t50 remained unchanged (Figure 3b). These results suggest that block extensions using Seed-6N3 proceeded regardless of the monomer ratios in the second block. The same experiments using Seed-63 instead of Seed-6N3 were conducted to produce NS-[63-b-(6N3+63)]-a. It is obvious from the AFM images that the roughness of the edges of the resulting nanosheets increased on increasing the proportion of 6N3 in the second block (Figure 3e). The values of s/Sn increased markedly when the ratio of 6N3 in the metastable nanoparticle was above 60% (Figure 3h). Under these conditions, the t50 values for the seeded growth kinetics were, indeed, significantly extended (Figure 3f). It is noteworthy that nanosheets, prepared with the same a value in the second block (for example, compare NS-[6N3-b-(6N3+63)]-60 and NS-[63-b-(6N3+63)]-60) in Figures 3a,e, have edges consisting of the same monomers but display different degrees of roughness. We believe that such structural variations at the mesoscopic scale in block copolymers created from the same molecular components through kinetically controlled self-assembly will pave the way to new functions and properties of supramolecular assemblies.[17b]    11  Figure 3. (a) AFM images of NS-[6N3-b-(6N3+63)] (bar = 500 nm): the proportions of 6N3 in the second block are shown under each AFM image. (b) t50, (c) Aw/An, (d) s/Sn, for the NS-[6N3-b-(6N3+63)] nanosheets. [Seed-6N3] = [NP-(6N3+63)] = 25 mM. (e) AFM images of NS-[6N3-b-(6N3+63)] (bar = 500 nm): the proportions of 6N3 in the second block are shown under each AFM image. (f) t50, (g) Aw/An, (h) s/Sn, for the NS-[63-b-(6N3+63)] nanosheets, [Seed-63] = [NP-(6N3+63)] = 25 mM.  0 20 40 60 80 100[6N3]/{[6N3]+[63]} (%)t 50 (min)Aw/Anσ /Sn0204060801001.01.11.21.31.41.500.010.020.040.060.070.030.05α = 0 50 60 70 80 10010 20 30 40 900 20 40 60 80 100[6N3]/{[6N3]+[63]} (%)0 20 40 60 80 100[6N3]/{[6N3]+[63]} (%)(a)(b) (c) (d)0 20 40 60 80 100[6N3]/{[6N3]+[63]} (%)t 50 (min)Aw/Anσ /Sn0204060801001.01.11.21.31.41.500.010.020.040.060.070.030.05α = 0 50 60 70 80 10010 20 30 40 900 20 40 60 80 100[6N3]/{[6N3]+[63]} (%)0 20 40 60 80 100[6N3]/{[6N3]+[63]} (%)(e)(f) (g) (h)NS-[6N3-b-(6N3+63)]-αNS-[63-b-(6N3+63)]-αrough edge rough edge rough edge[6N3]/{[6N3]+[63]} (%)[6N3]/{[6N3]+[63]} (%) 12 Conclusion In conclusion, we have demonstrated that the order of polymerization affects the structure of 2D block supramolecular copolymers in a manner similar to that observed in syntheses of conventional covalent block copolymers. Unlike one-dimensional living polymers, two-dimensional supramolecular polymers (or nanosheets) have two distinct propagation sites. We showed that inverting the order of polymerization can lead to distinct growth modes; importantly, secondary nucleation is involved in one of these cases. This secondary nucleation occurs slowly and sporadically; but once it occurs, the subsequent block extension is initiated from that point (i.e., the secondary nuclei), which, in turn, leads to the formation of roughened edges. From a different point of view, control over the shape (or edge roughness) of 2D nanosheets might be useful when designing functional materials that require large circumferences (or roughened edges). In addition, alkene (in 62), alkyne (in 63), and azide groups (in 6N3) introduced in our porphyrin-based monomers are well-known chemical handles for subsequent modifications of the products of supramolecular polymerization. For example, we previously demonstrated that azide groups on 2D supramolecular nanosheets can participate in click reactions in situ.[8c] We therefore believe that this study suggests a new strategy for the synthesis of functional block supramolecular nanosheets. Supporting Information Supporting information for this article is available online at Acknowledgements The work is supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI grant no. JP22H02134 (K.S); no. JP23K17941 (K.S.); and JP24H01712 (K.S.) in a Grant-in-Aid Scientific Research for Transformative Research Areas (A) “Materials Science of Meso-Hierarchy”; and by Japan Science and Technology Agency (JST) grant no. JPMJCR23L2 (K.S.) in Precise Material Science for Degradation and Stability, CREST. K.S. acknowledges financial support from The Murata Science Foundation, Sekisui Chemical Grant Program, and The Mitsubishi Foundation, The Samco Foundation. 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