# Fileset

[suppmat.pdf](https://mdr.nims.go.jp/filesets/66c186ce-42cf-4d1d-a4db-2d16c6af0cdd/download)

## Creator

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/)

## Other metadata

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

## Fulltext

SI1    Table of contents   Materials and Methods……………….………………………...…. 2 Syntheses and Characterizations 1. Synthesis of compound 62……………………………… 3 2. Synthesis of compound 63……………………………… 4 Supplementary Figures………………………………………..….. 7 Supplementary References……………………………………..… 11     2 Materials and Methods  Unless otherwise noted, reagents and solvents were purchased from commercial suppliers and used without further purification. Air- and/or water-sensitive reactions were conducted under argon atmosphere using dry solvents. Compound S1 were prepared according to the reported procedures.[1] Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL ECS-400 (400 MHz) and JEOL ECZ-600 (600 MHz) spectrometer. All chemical shifts are reported in parts per million (ppm) from tetramethylsilane (0 ppm for 1H) or residual CHCl3 (77 ppm for 13C) as an internal standard. Melting points were determined with a Yanako NP-500P micro melting point apparatus. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra were obtained using a Shimadzu Maldi-8030. Ultraviolet–visible absorption spectra were recorded using a quartz cuvette of 1.0 cm or 1 mm path length on a Jasco V-730, V-670 and V-630 spectrophotometer equipped with a Jasco ETCS-761 cell holder for temperature control. Spin-coating was performed using a Oshigane SC-300. Atomic force microscopy (AFM) was performed on a Bruker Dimension Icon atomic force microscope under ambient conditions in the scan assist analysis. AFM images were analyzed with Bruker Nanoanalysis and ImageJ.      3 Syntheses and Characterizations  1. Synthesis of compound 62  Synthesis of (62): A mixture of S1 (21 mg, 0.00840 mmol), 6-bromo-1-hexene (55.0 µL, 0.416 mmol) and K2CO3 (39.0 mg, 0.282 mmol) in DMF (6 mL) and THF (5 mL) was refluxed at 70 ºC for 12 h under argon atmosphere. Then, the crude was cooled to room temperature, diluted with CH2Cl2, then the organic layer was washed with water, dried over Na2SO4. The solvent was evaporated, and the obtained solid was purified by silica gel column chromatography (CHCl3/acetone = 15/1) and further by recycling gel permeation chromatography (CHCl3) to yield 62 as a purple solid (18.1 mg, 67.7%). m.p. = 90-94 ºC, 1H-NMR (600 MHz, CDCl3): d 0.80-0.89 (m, 18H, CH3-(CH2)10- CH2-O-, CH3-(CH2)16-CH2-O-), 1.09-1.33 (m, 120H, CH3-(CH2)8-CH2-CH2-CH2-O-, CH3-(CH2)14-CH2-CH2-CH2-O-), 1.41-1.47 (m, 12H, CH3-(CH2)8-CH2-CH2-CH2-O-, CH3-(CH2)14-CH2-CH2-CH2-O-), 1.70-1.82 (m, 16H, CH3-(CH2)8-CH2-CH2-CH2-O-, CH3-(CH2)14-CH2-CH2-CH2-O-, CH2=CH-CH2-CH2-CH2-CH2-O-), 1.99-2.04 (m,4H, CH2=CH-CH2-CH2-CH2-CH2-O-), 2.24-2.35 (m, 8H, CH2=CH-CH2-CH2-CH2-CH2-O-, -NH-CH2-CH2-CH2-O-), 3.81-3.86 (m, 4H, -NH-CH2-CH2-CH2-O-), 3.99 (t, J = 6.5 Hz, 4H, CH3-(CH2)16-CH2-O-), 4.02 (t, J = 6.5 Hz, 8H, CH3-(CH2)10-CH2-O-), 4.30 NNN NZnHN OONHOOOOORROOOC6H13C6H1362 : R = O63 : R = OS1 : R = OH  4 (t, J = 6.3 Hz, 4H, CH2=CH-CH2-CH2-CH2-CH2-O-), 4.44 (t, J = 5.4 Hz, 4H, -NH-CH2-CH2-CH2-O-), 5.04-5.07 (m, 2H, CH2=CH-CH2-CH2-CH2-CH2-O-), 5.11-5.16 (m, 2H, CH2=CH-CH2-CH2-CH2-CH2-O-), 5.90-5.98 (m, 2H, CH2=CH-CH2-CH2-CH2-CH2-O-), 6.71 (t, J = 5.5 Hz, 2H, -NH-), 8.11 (d, J = 8.4 Hz, 4H, C6H4), 8.13 (d, J = 8.0 Hz, 4H, C6H4), 8.94 (d, J = 4.6 Hz, 4H, b-pyrrole), 8.98 (d, J = 4.6 Hz, 4H, b-pyrrole).; 13C-NMR (101 MHz, CDCl3): d 14.10, 14.12, 22.64, 22.69, 25.52, 26.09, 28.97, 29.16, 29.29, 29.36, 29.38, 29.57, 29.60, 29.66, 29.73, 30.33, 31.87, 31.92, 33.58, 38.59, 67.26, 68.04, 69.40, 73.50, 105.60, 112.49, 114.82, 120.44, 120.84, 128.79, 129.54, 130.92, 131.74, 131.97, 135.05, 135.37, 135.50, 135.76, 138.61, 141.14, 150.37, 150.52, 153.14, 158.22, 158.74, 167.43.; Maldi-TOF mass (Dithanol): calcd. for C160H234N6O12Zn: 2500.75; found: 2501.43.   2. Synthesis of compound 63 Synthesis of (63): A mixture of S1 (25 mg, 0.0100 mmol), 6-bromo-1-hexyne (60.0 µL, 0.454 mmol) and K2CO3 (35.0 mg, 0.253 mmol) in DMF (2.4 mL) and THF (1.5 mL) was refluxed at 70 ºC for 17 h under argon atmosphere. Then, the crude was cooled to room temperature, diluted with CH2Cl2, then the organic layer was washed with water, dried over Na2SO4. Solvent was evaporated, and the obtained solid was purified by silica gel column chromatography (CHCl3/acetone = 15/1) and further by recycling gel permeation chromatography (CHCl3) to yield 63 as a purple solid (21.3 mg, 79.7%).   m.p. = 90-92 ºC, 1H-NMR (400 MHz, CDCl3): d 0.80-0.89 (m, 18H, CH3-(CH2)10- CH2-O-, CH3-(CH2)16-CH2-O-), 1.09-1.33 (m, 120H, CH3-(CH2)8-CH2-CH2-CH2-O-, CH3-(CH2)14-CH2-CH2-CH2-O-), 1.40-1.48 (m, 12H, CH3-(CH2)8-CH2-CH2-CH2-O-, CH3-(CH2)14-CH2-CH2-CH2-O-), 1.69-1.84 (m, 12H, CH3-(CH2)8-CH2-CH2-CH2-O-, CH3-(CH2)14-CH2-CH2-CH2-O-), 1.88-1.96 (m,4H, CH≡C-CH2-CH2-CH2-CH2-O-), 2.04-2.06 (m, 2H, CH≡C-CH2-CH2-CH2-CH2-O-), 2.09-2.17 (m, 4H, -NH-CH2-CH2-CH2-O-), 2.30-2.37 (m, 4H, -NH-CH2-CH2-CH2-O-), 2.40-2.45 (m, 4H, CH≡C-CH2-CH2-CH2-CH2-O-), 3.82-3.87 (m, 4H, -NH-CH2-CH2-CH2-O-), 3.99 (t, J = 6.5 Hz, 4H, CH3-(CH2)16-CH2-O-), 4.02 (t, J = 6.5 Hz, 8H, CH3-(CH2)10-CH2-O-), 4.30 (t, J = 6.1 Hz, 4H, CH≡C-CH2-CH2-CH2-CH2-O-), 4.44 (t, J = 5.4 Hz, 4H, -NH-CH2-CH2-CH2-O-), 6.71 (t, J = 5.5 Hz, 2H, -NH-), 8.10 (d, J = 8.1 Hz, 4H, C6H4), 8.13 (d, J = 8.0 Hz, 4H, C6H4), 8.95 (d, J = 4.7 Hz, 4H, b-pyrrole), 8.98 (d, J = 4.7 Hz, 4H, b-pyrrole).; 13C-NMR (101 MHz, CDCl3): d 14.10, 14.14, 18.31, 22.64, 22.68, 25.25, 26.09, 28.53, 29.16, 29.29, 29.38, 29.39, 29.57, 29.60, 29.67, 29.73, 30.32, 31.86, 31.92, 38.54, 67.26, 67.55, 68.75, 69.40, 73.50, 84.17, 105.60, 112.53, 120.43, 120.82, 129.52, 131.76, 131.94, 135.18, 135.40, 135.49, 135.80, 141.14, 150.39, 150.51, 153.11, 158.20, 158.66, 167.44.; Maldi-TOF mass (Dithanol): calcd. for C160H238N6O12Zn: 2496.72; found: 2495.98.       5   Figure S1. 1H NMR spectra of 62 and 63 in CDCl3 at 298 K.     6   Figure S2. 13C NMR spectra of 62 and 63 in CDCl3 at 298 K.   7 Supplementary Figures  Seed-62, Seed-63, and Seed-6N3 were prepared according to the procedure described below.   Seed-62 and Seed-63: First, thermodynamically stable nanosheets consisting of each monomer were prepared under ambient condition, by spontaneous conversion from the corresponding metastable nanoparticles (NP-62 and NP-63) in methyl cyclohexane (MCH) at room temperature. We then subjected the obtained nanosheets to sonication at 20 °C for 20 and 15 min, respectively, resulting in small fragments of nanosheets (referred to as Small seed-62 and Small seed-63, respectively, in Figure S3). Upon mixing these seeds with NP-62 and NP-63, we obtained Seed-62 and Seed-63 with controlled areas and narrow area distributions, which were used for subsequent supramolecular homopolymerization and heteropolymerization.   Seed-6N3: We directly applied a sonication to a solution of NP-6N3 in MCH at 30°C for 4 hours, and obtained small fragments of nanosheets consisting of 6N3, which is referred to as Small seed-6N3 in Figure S3. Upon mixing Small seed-6N3 with NP-6N3, we obtained Seed-6N3 with a controlled area and narrow area distribution, which were used for subsequent supramolecular homopolymerization and heteropolymerization.      8    Figure S3. (a,b,d,e,g,h) AFM images of (a) Small seed-6N3, (b) Seed-6N3, (d) Small seed-63, (e) Seed-63, (g) Small seed-62, (h) Seed-62. (c,f,i) Histograms of area of Small seed and Seed consisting of (c) 6N3, (f) 63, and (i) 62.   Seeded homopolymerization: Seed and Nanoparticle (NP) were mixed in MCH: [Small seed-6N3] : [NP-6N3] = 5 µM : 25 µM, [Small seed-63] : [NP-63] = 2.5 µM : 25 µM, [Small seed-62] : [NP-62] = 2.5 µM : 25 µM with respect to the concentration of porphyrins.  Small seed-6N3: An=11700 nm2, Aw/An=1.32; Seed-6N3: An = 57100 nm2, Aw/An=1.14. Small seed-63: An=4750 nm2, Aw/An=1.73; Seed-63: An = 34000 nm2, Aw/An=1.31. Small seed-62: An=9190 nm2, Aw/An=1.77; Seed-62: An = 58700 nm2, Aw/An=1.35.   0204060801001.0E+02 1.0E+03 1.0E+04 1.0E+05 1.0E+06Cumulation number102 103 104 105Area (nm2)Small seed-63 Seed-63106Small seed-6N30204060801001.0E+02 1.0E+03 1.0E+04 1.0E+05 1.0E+06Cumulation number102 103 104 105 106Area (nm2)Small seed-6N3 Seed-6N3Small seed-63Small seed-620204060801001.0E+02 1.0E+03 1.0E+04 1.0E+05 1.0E+06Cumulation number102 103 104 105 106Area (nm2)Small seed-62 Seed-62Seed-6N3(c)(b)(a)(d) (e) (f)Seed-63Seed-62(g) (h) (i)  9    Figure S4. (a,b) Absorption spectral changes observed during seeded homo-polymerization, Seed and NP were mixed in MCH solution: (a) [Seed-63] = [NP-63] = 25 µM, (b) [Seed-62] = [NP-62] = 25 µM, with respect to the concentration of porphyrin monomer. (Inset) Changes in the absorbance at 550 nm as a function of time. (c) Absorption spectra of Seed-6N3, Seed-63, and Seed-62.     0.00.20.40.60.81.01.2380 400 420 440 460 480AbsorbanceWavelength (nm)442 nm442 nm 444 nm391 nm391 nm393 nmSeed-6N3Seed-63Seed-620.00.20.40.60.81.01.2520 540 560 580 600 620AbsorbanceWavelength (nm)0.80.91.01.11.20 15 30Abs. at 550 nmTime (min)0.00.20.40.60.81.01.2520 540 560 580 600 620AbsorbanceWavelength (nm)0.80.91.01.10 15 30Abs. at 550 nmTime (min)(a) (b)(c)Seed-62  10    Figure S5. (a,b) Kinetics profiles of the homopolymerization and heteropolymerization depending on nanoparticles concentration: (a) Seed-6N3 + NP-6N3, (b) Seed-63 + NP-63, (c) Seed-6N3 + NP-63, (d) Seed-63 + NP-6N3. In all cases, [Seed] = 25 µM, with respect to porphyrin concentration, and changes in absorbance were observed at 550 nm. Changes in absorbance and normalized changes in absorbance are shown in left and right, respectively.    0.00.10.20.30.40 10 20 30 40DAbsorbanceTime (min)1:1.6 1:1.21:0.81:0.4Seed-6N3 : NP-6N300.10.20.30 20 40 60DAbsorbanceTime (min)1:1.61:1.21:0.81:0.4Seed-63 : NP-6300.10.20.30 10 20 30 40 50DAbsorbanceTime (min)1:1.61:1.2 1:0.81:0.4Seed-6N3 : NP-6300.10.20.30 30 60 90 120DAbsorbanceTime (min)1:0.81:0.61:0.51:0.4Seed-63 : NP-6N30.00.20.40.60.81.00 10 20 30 40NormalizedDabsorbanceTime (min)Seed-6N3 : NP-6N31 : 1.61 : 1.21 : 0.81 : 0.40.00.20.40.60.81.00 20 40 60NormalizedDabsorbanceTime (min)Seed-63 : NP-631 : 1.61 : 1.21 : 0.81 : 0.4Seed-6N3 : NP-631 : 1.61 : 1.21 : 0.81 : 0.40.00.20.40.60.81.00 10 20 30 40 50NormalizedDabsorbanceTime (min)(b)(c)(a)(d)Seed-63 : NP-6N31 : 0.81 : 0.61 : 0.51 : 0.40.00.20.40.60.81.00 30 60 90 120NormalizedDabsorbanceTime (min)  11    Figure S6. AFM images of (a) NS-(62-62), NS-(62-b-63), NS-(63-b-62), NS-(6N3-b-62), and NS-(62-b-6N3) (bar=500nm). (b) Changes in the absorbance observed during homo- and hetero-seeded polymerizations. (c) Values of t50 for the seeded growth process, determined from (b). (d) Aw/An values, (e) Sn, and (f) s/Sn for the obtained nanosheets.    Supplementary References   [1] a) T. Fukui, S. Kawai, S. Fujinuma, Y. Matsushita, T. Yasuda, T. Sakurai, S. Seki, M. Takeuchi, K. Sugiyasu, Nat. Chem. 2017, 9, 493; b) Z. Jin, N. Sasaki, N. Kishida, M. Takeuchi, Y. Wakayama, K. Sugiyasu, Chem. Eur. J. 2023, 29, e202302181.   0102030NS-(62-b-62)NS-(62-b-63)NS-(63-b-62)NS-(6N3-b-62)NS-(62-b-6N3)t 50NS-(62-62)NS-(62-b-6 3)NS-(6N 3-b-6 2)NS-(62-b-6N3)NS-(63-b-6 2)Seed-63+NP-62Seed-62+NP-62Seed-62+NP-63Seed-62+NP-6N3Seed-6N3+NP-620.00.20.40.60.81.01.20 10 20 30 40 50Normalized DabsorbanceTime (min)0.000.010.020.030.040.050.060.07NS-(62-b-62)NS-(62-b-63)NS-(63-b-62)NS-(6N3-b-62)NS-(62-b-6N3)s/S nNS-(62-62)NS-(62-b-6 3)NS-(6N 3-b-6 2)NS-(62-b-6N3)NS-(63-b-6 2)0.750.800.850.900.951.00NS-(62-b-62)NS-(62-b-63)NS-(63-b-62)NS-(6N3-b-62)NS-(62-b-6N3)S nNS-(62-62)NS-(62-b-6 3)NS-(6N 3-b-6 2)NS-(62-b-6N3)NS-(63-b-6 2)1.01.11.21.31.41.51.6NS-(62-b-62)NS-(62-b-63)NS-(63-b-62)NS-(6N3-b-62)NS-(62-b-6N3)Aw/A nNS-(62-62)NS-(62-b-6 3)NS-(6N 3-b-6 2)NS-(62-b-6N3)NS-(63-b-6 2)NS-(62-b-63)(b) NS-(62-62)(d)NS-(63-b-62) NS-(6N3-b-62) NS-(62-b-6N3)(e) (f)(c)(a)