Electronic Supplementary Material (ESI) for Nanoscale Horizons.
This journal is © The Royal Society of Chemistry 2024

Electronic Supplementary Material (ESI) for Nanoscale Horizons.
This journal is © The Royal Society of Chemistry 2024

Supplementary Information
Designing 2D Stripe Random Network Through Crown-Ether
Intermediate Ullmann Coupling on Cu(111) Surface

Toyo Kazu Yamada1,2*, Ryohei Nemoto1, Haruki Ishii1, Fumi Nishino1, Yu-Hsin
Chang3, Chi-Hsien Wang3, Peter Krüger1,2, Masaki Horie3
1. Department of Materials Science, Chiba University, 1-33 Yayoi-Cho, Inage-ku, Chiba 263-8522, Japan.
2. Molecular Chirality Research Centre, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
3. Department of Chemical Engineering, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu,
30013, Taiwan

Author Information,Corresponding Author: Toyo Kazu Yamada *E-mail: toyoyamada@faculty.chiba-u.jp
Version 2024.3.25 RCS styleFigure S1aCu(111)b

Br-CR array

Thermalannealing

10 nm

20 nm

Figure S1. (a) STM topographic image obtained at 77.8 K on the Cu(111) surface after BrCR island growthwithout annealing (100 × 100 nm2, -2.5 V, 10 pA). (b) STM topographic image obtained on theBrCR/Cu(111) surface after the thermal annealing at 453 K for 10 min (200×200 nm2, -2.5 V, 10 pA).

Figure S210 nm

10 nm

Figure S2. STM topographic images obtained on the BrCR/Cu(111) surface after the thermal annealing at433 K for 18 min (100×100 nm2, -2.5 V, 10 pA).

Figure S3Bright spots
Bright spots

5Density

43210-0.1

0.0

0.1

0.2
0.3
Proportional

0.40.55 nm

Figure S3. STM topographic image (50×50 nm2, -1.6 V, 100 pA). of the chains. Height profiles along thelines were used to evaluated numbers of the bright spots in each chain.

Figure S4Centroid [MS: 0.7536-0.8869] / 2022081960-256-2 / FD+(eiFi) / /(22313)

4x10

1191.9

2.25
2.00
1.75

Intensity

1.50
1.25
1.00
0.75
1271.8
0.50
0.25
0.00
250

500

750

1000

1250

1500m/z

Figure S4. FDMS of Ullmann coupling products. The reaction was conducted using 1 mg Br-CR
and 2 mg Cu powder at 260 ºC for 3h. The main peak at m/z = 1192 corresponds to [C40H40Br6O12+ H]+ = 1192. Plausible chemical structure is shown in the figure.

Figure S5Figure S5. FDMS of Ullmann coupling products. The reaction was conducted using 1 mg Br-CR
and 2 mg Cu powder at 260 ºC for 5h. The peaks at m/z = 1034, 1114, and 1192 suggest the presence+++of [C40H40Br4O12 + H] = 1033 or [C40H42Br4O12] = 1034, [C40H41Br5O12 + H] = 1113, and[C40H40Br6O12 + H]+ = 1192, respectively. Simulated isotope patterns and plausible chemicalstructures are shown in the figure.

Figure S6

Figure S6. FDMS of Ullmann coupling products. The reaction was conducted using 1 mg Br-CR
and 5 mg Cu powder at 260 ºC for 3h. The peaks at m/z = 1034, 1114, 1192, and 1550 suggest the++presence of [C40H40Br4O12 + H] = 1033 or [C40H42Br4O12] = 1034, [C40H41Br5O12 + H]+ = 1113,[C40H40Br6O12 + H]+ = 1192, and [C60H60Br6O18 + H]+ = 1549, respectively. Simulated isotopepatterns and plausible chemical structures are shown in the figure.

Figure S7

The reaction enreactant molec
monomers:
connection:connection:connection:connection:state No.1:
intermediate st(Fig. 4b).

Figure S7. Expected chemical reactions using the BrCR precursor molecules on the Cu(111) using
thermal annealing before performing the experiments.

Figure S8

Figure S8. Histogram of connection angles between precursors in the STM topographic c image ofFig .3a in the main text.

Figure S9

Figure S9. DFT calculated density of states (DOS) plots of all configurations in Fig. 2.