Electrostatically Driven Guest Binding in Self-Assembled Porous Network at the Liquid/Solid Interface

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1 Supporting Information for Electrostatically Driven Guest Binding in Self-Assembled Porous Network at the Liquid/Solid Interface Kohei Iritani,, Motoki Ikeda, Anna Yang, Kazukuni Tahara,, Masaru Anzai, Keiji Hirose, Steven De Feyter, Jeffrey S. Moore,, * Yoshito Tobe,, * Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka , Japan, Departments of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana Champaign, Urbana, Illinois 61801, United States, Department of Applied Chemistry, School of Science and Technology, Meiji University, Kawasaki, Kanagawa , Japan, Department of Chemistry, KU Leuven University of Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium. The Institute of Scientific and Industrial Research, Osaka University, 8-1, Mihogaoka, Ibaraki, Osaka , Japan Present address: Department of Applied Chemistry, School of Engineering, Tokyo University of Technology, Hachioji, Tokyo , Japan *To whom correspondence should be addressed. jsmoore@illinois.edu (J.S.M.); tobe@chem.es.osaka-u.ac.jp (Y.T.). S1

2 Contents 1. Additional STM Images and Molecular Models S3 2. Experimental Details for Synthesis of DBA-TeEG S H and 13 C Spectra of New Compounds S19 4. References S22 S2

3 1. Additional STM Images and Molecular Models Figure S1. Large area STM images of honeycomb structures formed by (a) DBA-TeEG ( M, I set = 28 pa and V set = 88 mv) and (b) DBA-C10 ( M, I set = 41 pa and V set = 200 mv) after annealing at 70 C for 1 h at the TCB/graphite interface. White dotted lines indicate domain boundaries. Figure S2. (a, b) STM images of monolayers formed by a mixture of DBA-TeEG ( M) and PEM-TEG ( M) before annealing treatment at the TCB/graphite interface (tunneling parameters: I set = 281 pa and V set = 141 mv). Unit cell parameters are a = b = 5.0 ± 0.1 nm, γ = 60 ± 1. White dotted lines in (a) and arrows in (b) indicate the domain boundaries and the directions of the main symmetry axes of underlying graphite, respectively. (c) The same STM images as (b), in which red, green, yellow, and white hexagons indicate filled pores, partly filled pores, fuzzy pores, and open pores, respectively. S3

4 Figure S3. (a, b) STM images of monolayers formed by a mixture DBA-TeEG ( M) and PEM-TEG ( M) before annealing treatment at the TCB/graphite interface (tunneling parameters: I set = 100 pa and V set = 90 mv for a, I set = 100 pa and V set = 70 mv for b). Unit cell parameters of the honeycomb structure of DBA-TeEG are a = b = 5.0 ± 0.1 nm, γ = 60 ± 1. White solid and dotted lines in (a) indicate the boundaries between domains of networks of DBA-TeEG and PEM-TEG, and those of DBA-TeEG. Arrows in (b) indicate the directions of the main symmetry axes of underlying graphite. (c) The same STM images as (b), in which red, green, and white hexagons indicate filled pores, partly filled pores, and open pores, respectively. S4

5 Figure S4. (a, b) STM images of monolayers formed by a mixture of DBA-TeEG ( M) and PEM-TEG ( M) after annealing at 70 C for 1 h at the TCB/graphite interface (tunneling parameters: I set = 24 pa and V set = 80 mv for a, I set = 92 pa and V set = 150 mv for b). Unit cell parameters of the honeycomb structure of DBA-TeEG are a = b = 5.0 ± 0.1 nm, γ = 60 ± 1. White lines in (a) indicate the boundaries between domains of networks of DBA-TeEG and PEM-TEG. White arrows in (b) indicate the directions of the main symmetry axes of underlying graphite. (c) The same STM images as (b), in which red, green, and white hexagons indicate filled pores, partly filled pores, and open pores, respectively. S5

and b) and after (c and d) annealing at 70 C for 1 h at the TCB/graphite interface (concentrations = 1.

6 10 5 M for PEM-TEG, tunneling parameters: I set = 100 pa and V set = 60 mv for a, I set = 100 pa and V set =

1 nm, γ = 60 ± 1 for dense hexagonal structure, and a = 2.2 ± 0.1 nm, b = 4.5 ± 0.

White lines and arrows indicate the boundaries between domains of networks of DBA-TeEG and PEM-TEG and the

6 Figure S5. STM images of domains of dense hexagonal (a and c) and zigzag (b and d) structures formed by PEM-TEG before (a and b) and after (c and d) annealing at 70 C for 1 h at the TCB/graphite interface (concentrations = M for DBA-TeEG and M for PEM-TEG, tunneling parameters: I set = 100 pa and V set = 60 mv for a, I set = 100 pa and V set = 70 mv for b, and I set = 24 pa and V set = 320 mv for c and d). Unit cell parameters are a = b = 2.6 ± 0.1 nm, γ = 60 ± 1 for dense hexagonal structure, and a = 2.2 ± 0.1 nm, b = 4.5 ± 0.1 nm, γ = 90 ± 1 for zigzag structure. White lines and arrows indicate the boundaries between domains of networks of DBA-TeEG and PEM-TEG and the directions of the main symmetry axes of underlying graphite, respectively. (c, d) Molecular models of dense hexagonal (c) and zigzag (d) structures formed by a PEM derivative bearing ethyl ester groups on a graphene bilayer (optimized by MM simulations under periodic boundary conditions (PBC): a = b = 2.13 nm, γ = 60.0º for the dense hexagonal structure, a = 2.13 nm, b = 4.43 nm, γ = 90.0º for the zigzag structure). S6

Figure S6. STM images of (a) the honeycomb structures formed by DBA-TeEG (1.0 10 5 M) and PEM-C6 (1.

mv for a, I set = 77 pa and V set = 300 mv for b). Unit cell parameters of the honeycomb structure of PEM-C6 are a = b = 4.7 ± 0.1 nm, γ = 60 ± 1.

Arrows in (b) indicate the directions of the main symmetry axes of underlying graphite.

7 Figure S6. STM images of (a) the honeycomb structures formed by DBA-TeEG ( M) and PEM-C6 ( M) and (b) the honeycomb structure of PEM-C6 after annealing at 70 C for 1 h at the TCB/graphite interface (tunneling parameters: I set = 72 pa and V set = 410 mv for a, I set = 77 pa and V set = 300 mv for b). Unit cell parameters of the honeycomb structure of PEM-C6 are a = b = 4.7 ± 0.1 nm, γ = 60 ± 1. White solid and dotted lines in (a) indicate the boundaries between domains of networks of DBA-TeEG and PEM-C6, and those of DBA-TeEG, respectively. Arrows in (b) indicate the directions of the main symmetry axes of underlying graphite. (c, d) Molecular models of honeycomb structures with co-adsorbed PEM-C6 molecules (green) whose alkyl chains adopt the same orientation (c) or the opposite orientation (d) as that of the inner periphery of the honeycomb structure (optimized by MM simulations on a graphene bilayer under periodic boundary conditions (PBC): a = b = 4.67 nm, γ = 60.0 ). S7

Figure S7. STM image of monolayer formed by PEM-C6 before annealing treatment at the TCB/graphite interface (concentrations = 1.0 10 5 M for DBA-TeEG and 1.

White arrows indicate the directions of the main symmetry axes of underlying graphite. Figure S8. (a, b) STM images of monolayers formed by a mixture of DBA-C10 (1.0 10 5 M) and PEM-TEG (1.

8 Figure S7. STM image of monolayer formed by PEM-C6 before annealing treatment at the TCB/graphite interface (concentrations = M for DBA-TeEG and M for PEM-C6, tunneling parameters: I set = 60 pa and V set = 190 mv). Unit cell parameters of the honeycomb structure of PEM-C6 are a = b = 4.7 ± 0.1 nm, γ = 60 ± 1. White arrows indicate the directions of the main symmetry axes of underlying graphite. Figure S8. (a, b) STM images of monolayers formed by a mixture of DBA-C10 ( M) and PEM-TEG ( M) before annealing treatment at the TCB/graphite interface (tunneling parameters: I set = 78 pa and V set = 240 mv). Unit cell parameters of the honeycomb structure of DBA-C10 are a = b = 5.0 ± 0.1 nm, γ = 60 ± 1. White dotted lines in (a) and arrows in (b) indicate domain boundaries of the honeycomb structure of DBA-C10 and the directions of the main symmetry axes of underlying graphite, respectively. (c) The same STM images as (b), in which red and white hexagons indicate filled pores and open pores, respectively. S8

9 Figure S9. (a, b) STM images of monolayers formed by DBA-C10 ( M) and PEM-TEG ( M) before annealing treatment at the TCB/graphite interface (tunneling parameters: I set = 100 pa and V set = 150 mv). Unit cell parameters of the honeycomb structure of DBA-C10 are a = b = 5.0 ± 0.1 nm, γ = 60 ± 1. White solid and dotted lines in (a) and arrows in (b) indicate domain boundaries between the monolayers of DBA-C10 and PEM-TEG, those of the honeycomb structure of DBA-C10, and the directions of the main symmetry axes of underlying graphite, respectively. (c) The same STM images as (b), in which red and white hexagons indicate filled pores and open pores, respectively. S9

before annealing treatment (a, b) and after annealing treatment at 70 C for 1 h (c, d) at the

6 10 5 M for PEM-TEG, tunneling parameters: I set = 100 pa and V set = 80 mv for a and b, I set =

Unit cell parameters are a = b = 2.6 ± 0.1 nm, γ = 60 ± 1 for dense hexagonal structure, and a = 2.

10 Figure S10. STM images of the domains of dense hexagonal (a, c) and zigzag (b, d) structures formed by PEM-TEG before annealing treatment (a, b) and after annealing treatment at 70 C for 1 h (c, d) at the TCB/graphite interface (concentrations = M for DBA-C10 and M for PEM-TEG, tunneling parameters: I set = 100 pa and V set = 80 mv for a and b, I set = 52 pa and V set = 370 mv for c, I set = 52 pa and V set = 420 mv for d). Unit cell parameters are a = b = 2.6 ± 0.1 nm, γ = 60 ± 1 for dense hexagonal structure, and a = 2.2 ± 0.1 nm, b = 4.5 ± 0.1 nm, γ = 90 ± 1 for zigzag structure. White lines and arrows indicate the boundaries between domains of networks of DBA-C10 and PEM-TEG and the directions of the main symmetry axes of underlying graphite, respectively. S10

11 Figure S11. (a) STM image of monolayers formed by DBA-C10 ( M) and PEM-C6 ( M) before annealing treatment at the TCB/graphite interface (tunneling parameters: I set = 72 pa and V set = 160 mv). Unit cell parameters are a 1 = b 1 = 5.0 ± 0.1 nm, γ 1 = 60 ± 1 for the honeycomb structure of DBA-C10, and a 2 = b 2 = 4.7 ± 0.1 nm, γ 2 = 60 ± 1 for the honeycomb structure of PEM-C6. White solid and dotted lines, and arrows indicate boundaries between the domains of networks of DBA-C10 and PEM-C6, those of the honeycomb structure of DBA-C10, and the directions of the main symmetry axis of underlying graphite, respectively. (b) The same STM images as (a), in which yellow and white hexagons indicate fuzzy pores and open pores, respectively. S11

0 10 5 M) after annealing at 70 C for 1 h at the TCB/graphite interface (tunneling parameters: I set = 72

12 Figure S12. STM images of monolayer formed by PEM-C6 obtained using a mixture of DBA-C10 and PEM-C6 (each M) after annealing at 70 C for 1 h at the TCB/graphite interface (tunneling parameters: I set = 72 pa and V set = 280 mv). Unit cell parameters of the honeycomb structure of PEM-C6 are a = b = 4.7 ± 0.1 nm, γ = 60 ± 1. White arrows indicate the directions of the main symmetry axes of underlying graphite. S12

97 nm, γ = 60 ) on a bilayer graphene for monolayers formed by a mixture of DBA-TeEG and PEM-C6.

orientation with respect to the TeEG units of DBA-TeEG.

(c) The TeEG units of DBA-TeEG being desorbed and the C 6 chains of PEM-C6 adopting the same (ACW) (d)

13 Figure S13. Molecular models optimized by COMPASS force field under periodic boundary conditions (a = b = 4.97 nm, γ = 60 ) on a bilayer graphene for monolayers formed by a mixture of DBA-TeEG and PEM-C6. (a) The TeEG units of DBA-TeEG being adsorbed and the C 6 chains of PEM-C6 adopting the same (ACW) orientation with respect to the TeEG units of DBA-TeEG. (b) The TeEG units of DBA-TeEG being adsorbed and the C 6 chains of PEM-C6 adopting the opposite (CW) orientation with respect to the TeEG units of DBA-TeEG. (c) The TeEG units of DBA-TeEG being desorbed and the C 6 chains of PEM-C6 adopting the same (ACW) orientation with respect to the TeEG units of DBA-TeEG. (d) The TeEG units of DBA-TeEG being desorbed and the C 6 chains of PEM-C6 adopting the opposite (CW) orientation with the respect to the TeEG units of DBA-TeEG. S13

14 Figure S14. Molecular models optimized by COMPASS force field under periodic boundary conditions (a = b = 4.97 nm, γ = 60 ) on a bilayer graphene for the honeycomb structures formed by DBA-TeEG (a) and DBA-C10 (b) with seven molecules of TCB in the pores. S14

15 Table S1. Intermolecular Energies for Host-TCB Systems on Bilayered Graphene Sheet Calculated by MM Simulations Using COMPASS Force Field under Periodic Boundary Conditions (a = b = 4.97 nm, γ = 60.0º) system intermolecular energy a (kcal/mol) b c E total E host E TCB E host-tcb d (kcal/mol) DBA-TeEG/7 TCB DBA-C10/7 TCB a Sum of the intermolecular and molecule-substrate interaction energies. b E host was obtained by single point energy calculations for the host-guest systems in their optimized geometries which do not contain the guest molecules. c E TCB was obtained by single point energy calculations for the host-guest systems in their optimized geometries which do not contain the host networks. d Calculated by the following equation, E host-tcb = E total E host E TCB. S15

16 2. Experimental Details for Synthesis of DBA-TeEG 2.1. General All manipulations were performed under an inert gas (nitrogen or argon) atmosphere. All solvents were distilled or passed through active alumina and copper catalyst in a Glass Contour solvent purification system before use. All commercially available reagents were used as received. Compound 1 1 and 4 2 were prepared according to the reported procedure. 1 H (400 MHz) and 13 C (100 MHz) NMR spectra were measured on a Bruker UltraShield Plus 400 spectrometer using chloroform-d as a solvent. The spectra were referenced to residual solvent proton signals in the 1 H NMR spectra (7.26 ppm) and to the solvent carbon signals in the 13 C NMR spectra (77.0 ppm). Preparative GPC separation was undertaken with a JAI LC-908 and JAI LC-9204 recycling chromatographs using 600 mm 20 mm JAIGEL-1H and 2H (for JAI LC-908) or 600 mm 40 mm JAIGEL-1H-40 and 2H-40 (for JAI LC-9204) GPC columns with CHCl 3 as the eluent. Other spectra were recorded by the use of the following instruments: IR spectra, JACSCO FT/IR-410; mass spectra, JEOL JMS-700 in FAB ionization mode Synthesis of DBA-TeEG. S16

17 Compound 2. 1,4-Dihydroxybenzene (1.01 g, 9.25 mmol), K 2 CO 3 (1.92 g, 14.0 mmol), and MeCN (40 ml) were added to a three-necked flask. After addition of 1 1 (1.61 g, 4.62 mmol), the mixture was heated under reflux for 9 h. After removal of precipitated solid by filtration and the solvent was evaporated under vacuum. The residue was passed through a short column chromatography (silica gel, MeCN). The crude product mixture was subjected to a silica gel column chromatography (EtOAc/MeCN = from 150/1 to 30/1). Further purification was performed by recycling GPC (CHCl 3 ) to give 2 (378 mg, 30%) as a brown oil. 1 H NMR (400 MHz, CDCl 3, 30 C) δ (m, 4H), 5.53 (br s, 1H), 4.03 (t, J = 4.8 Hz, 2H), 3.80 (t, J = 4.8 Hz, 2H), (m, 10H), 3.60 (t, J = 4.8 Hz, 2H); 13 C NMR (100 MHz, CDCl 3, 30 C) δ 152.0, 150.0, 115.9, 115.6, 72.3, 70.37, 70.36, 70.3, 69.9, 69.7, 67.9, 61.4; IR (NaCl) 3364, 3032, 2921, 2875, 1512, 1455, 1351, 1233, 1103, 1065, 945, 829, 756 cm 1 ; HRMS (FAB): m/z calcd for C 14 H 22 O 6 (M + ): , found: Compound 3. A solution of 2 (199 mg, 696 µmol) in CH 2 Cl 2 was added to a three-necked flask and the solvent was removed under vacuum. K 2 CO 3 (106 mg, 766 µmol), 1,10-dibromodecane (640 µl, 2.85 mmol), and DMF (13 ml) were added. The mixture was stirring at 50 C for 12 h, and then at 60 C for 5 h. Additional K 2 CO 3 (19.5 mg, 141 µmol) was added and the mixture was further stirred at 60 C for 2 h, before water was added. The product was extracted with Et 2 O, and the organic phase was dried over MgSO 4. After removal of the solvents under vacuum, of the product was subjected to silica gel column chromatography (EtOAc/hexanes = 6/1). Further purification was performed by precipitation from CH 2 Cl 2 /hexanes to afford 3 (80.5 mg, 25%) as a white solid. mp C; 1 H NMR (400 MHz, CDCl 3, 30 C) δ (m, 4H), 4.08 (t, J = 4.8 Hz, 2H), 3.89 (t, J = 6.4 Hz, 2H), 3.83 (t, J = 4.8 Hz, 2H), (m, 10H), 3.61 (t, J = 4.4 Hz, 2H), 3.41 (t, J = 6.8 Hz, 2H), 1.86 (quint, J = 7.2 Hz, 2H), 1.75 (quint, J = 6.4Hz, 2H), (m, 12H); 13 C NMR (100 MHz, CDCl 3, 30 C) δ 153.5, 152.8, 115.6, 115.4, 72.5, 70.7, 70.64, 70.58, 70.3, S17

18 69.9, 68.6, 68.1, 61.8, 34.0, 32.8, 29.4, 29.34, 29.31, 28.7, 28.1, 26.0; IR (KBr) 3410, 2934, 2921, 2853, 1511, 1475, 1395, 1353, 1280, 1243, 1135, 1064, 1016, 926, 825, 758, 646 cm 1 ; HRMS (FAB): m/z calcd for C 24 H BrO 6 (M + ): , found: DBA-TeEG. A solution of 4 2 (13.4 mg, 13.6 µmol) in CH 2 Cl 2 was added to a Schlenk flask and the solvent was removed under vacuum. DMF (1.0 ml), K 2 CO 3 (9.9 mg, 71 µmol), and 3 (35.4 mg, 70.0 µmol) were added. After stirring at 60 C for 18 h, additional K 2 CO 3 (1.6 mg, 12 µmol) was added to the mixture. After stirring at 60 C for 15 h, the solvent was removed under vacuum. The residue was passed through a short column chromatography (silica gel, CH 2 Cl 2 ). The product was purified by silica gel column chromatography (CH 2 Cl 2 /MeOH = 22/1), and further purification was performed by recycling GPC (CHCl 3 ) to give DBA-TeEG (12.3 mg, 40%) as a yellow solid. mp C; 1 H NMR (400 MHz, CDCl 3, 30 C) δ (m, 12H), 6.72 (s, 6H), 4.08 (m, 6H), 3.95 (t, J = 6.8 Hz, 12H), 3.89 (t, J = 6.8 Hz, 6H), 3.83 (m, 6H), (m, 30H), 3.61 (m, 6H), (m, 18H), (m, 102H), 0.88 (t, J = 6.8 Hz, 9H); 13 C NMR (100 MHz, CDCl 3, 30 C) δ 153.5, 152.8, 149.2, 119.8, 115.8, 115.7, 115.4, 91.9, 72.5, 70.8, 70.7, 70.6, 70.4, 69.9, 69.1, 68.6, 68.2, 61.8, 29.70, 29.66, 29.6, 29.5, 29.44, 29.42, 29.37, 29.36, 29.1, 26.1, 26.0, 22.7, 14.1; IR (KBr) 3393, 2920, 2851, 1592, 1508, 1467, 1348, 1227, 1124, 1068, 1012, 862, 822, 721 cm 1 ; HRMS (FAB): m/z calcd for C 138 H 216 O 24 (M + ): , found: S18

19 3. 1 H and 13 C Spectra of New Compounds Figure S15. 1 H and 13 C NMR spectra of 2 in CDCl 3 at 30 C. S19

20 Figure S16. 1 H and 13 C NMR spectra of 3 in CDCl 3 at 30 C. S20

21 Figure S17. 1 H and 13 C NMR spectra of DBA-TeEG in CDCl 3 at 30 C. S21

22 4. References (1) Xie, H. Z.; Braha, O.; Gu, L.-Q.; Cheley, S.; Bayley, H. Single-Molecule Observation of the Catalytic Subunit of camp-dependent Protein Kinase Binding to an Inhibitor Peptide. Chem. Biol. 2005, 12, (2) Tahara, K.; Yamaga, H.; Ghijsens, E.; Inukai, K.; Adisoejoso, J.; Blunt, M. O.; De Feyter, S.; Tobe, Y. Control and Induction of Surface-Confined Homochiral Porous Molecular Networks. Nat. Chem. 2011, 3, S22

Supporting Information for

Supporting Information for Odd-Even Effects in Chiral Phase Transition at the Liquid/Solid Interface Hai Cao, a Kazukuni Tahara, bc Shintaro Itano, b Yoshito Tobe b* and Steven De Feyter a* a Division