Dendritic Structure Having a Potential Gradient - ACS Publications

A Dendritic Structure Having a Potential Gradient: New Synthesis and Properties of Carbazole Dendrimers Ken Albrecht and Kimihisa Yamamoto* Department of Chemistry, Faculty of Science & Technology, Keio University, Yokohama 223-8522, Japan [email protected] Supporting Information Table of Contents 1. Experimental section

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2. Synthesis

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2-1. Carbazole dendrons (CzGnon)

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2-2. Benzene substituted carbazole dendrons (GnPh)

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2-3. Benzophenone and phenylazomethine substituted carbazole dendrons (GnB, and GnA)

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2-4. Ferrocene substituted carbazole dendrons (GnFc)

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3. Generation-hydrodynamic radius plot

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4. UV-absorption spectra of G1B

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5. Fluorescence spectra of CzGnon

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6. MOPAC calculated molecular models

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7. Substituent effect of carbazole

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8. RedOx potential of GnFc

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9. UV-vis titration

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10. Assignment of the NMR spectra (GnFc)

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11. Molecular models (Gaussian calculation)

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12. Crystal Structure Determination

S38

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1. Experimental section Chemicals. Carbazole was purchased from the Kanto Kagaku Co. and recrystallized once from toluene before use. All other reagents were purchased from the Kanto Kagaku Co., Aldrich, Tokyo Kasei Co., WAKO chemicals, Acros Organics, and Alfa Aesar and used without further purification. Dioxane for the reaction, benzene and acetonitrile for the UV-vis titration, and 1,2-dichloroethane and benzonitrile for the electrochemical measurements were all the dehydrated grades. All the synthesized compounds were reprecipitated from hexane with chloroform and dried in vacuo before use in the next reaction or measurement. General. The NMR spectra were obtained using a JEOL JNM-EX270 (270MHz), a JEOL JNM-GX400 (400MHz), and a JNM-AL400 (400MHz) with TMS as the internal standard. The NMR spectra of the carbazole dendrons (CzGnon) had strong concentration dependence, therefore, the concentration of the solution that was used for the measurement was marked (see the synthesis section). The MALDI TOF-MS data were obtained using a KOMPACT MALDI mass spectrometer (Shimadzu/Kratos) in the positive ion mode. Dithranol was used as the matrix. The elemental analysis was performed at the Central Service Facilities for Research of Keio University. A preparative scale gel permeation chromatograph, LC-908 (Japan Analytical Industry Co., Ltd.), was used to isolate each compound with chloroform as the eluent. The UV-vis spectra were recorded using a Shimadzu UV-3150 spectrometer with a quartz cell having a 1cm optical length at 20℃. The fluorescence spectra were recorded by a JASCO FP-6500 spectrofluorometer with a quartz cell having a 1cm optical length. The IR spectra were recorded using a JASCO FT/IR-460PLUS spectrometer with a KBr pellet or KBr window liquid cell having a 1mm optical length. The electrochemical measurements were done using a conventional three-electrode configuration with an ALS Chi660 electrochemical analyzer. The counter and reference electrodes were a Pt wire and Ag/Ag+, respectively. The solvent was 1,2-dichloroethane (GnPh, GnB) or benzonitrile (GnFc), the concentration of the sample was 0.5mM (GnPh, GnB) or 1mM (GnFc), and the supporting electrolyte was 0.2M tetra-n-butylammonium perchlorate (TBAP). The solution was purged with nitrogen before the measurements. The increased voltage was 0.004v, the amplitude was 0.05V, the pulse width was 0.06s, the sample width was 0.02s, and the pulse period was 0.2s for the DPV measurements. Analytical size-exclusion chromatography (SEC) was performed using an HPLC (Shimadzu, LC-10AP) equipped with a TSK-GEL CMHXL (Tosoh) at 40℃. Tetrahydrofuran (THF) was used as the eluent at the flow rate of 1 S2

mL/min. The detection line was connected to a triple detector (refractive index, light scattering, and viscosity. Viscotek, TriSEC model 302). 2. Synthesis 2-1. Carbazole dendrons (CzGnon)

Reagents & Conditions: (a) CuI, trans-1,2-cyclohexanediamine, K3PO4, dioxane, 110℃, 24h (b) TFA, toluene, water, anisole, 72h, r.t., 12h.

9-Boc-3,6-diiodocarbazole (I2BocCz).

A mixture of carbazole (30g, 174mmol) and acetic acid (500ml) was

heated to ca.100℃ then stirred until the carbazole had completely dissolved. The flask was removed from the oil bath and finely-crushed potassium iodide (39g, 235mmol) was added. After a few minutes of stirring, potassium iodate (57g, 266mmol) was carefully added in small increments. The mixture was then refluxed for 15 minutes, cooled to 0℃, and an aqueous sodium thiosulfate solution was added until the color of the iodine disappeared. The precipitate was filtered, washed with aqueous sodium thiosulfate, sodium hydrogen carbonate, and water. To the precipitate, toluene (1000ml) was added and sonicated to dissolve the soluble part, and then filtered through silica gel and the filtrate was concentrated. Acetone (500ml) was next added and the insoluble compounds were filtered away. To this solution, di-tert-butyl dicarbonate (50ml, 217mmol) was first added, and then 4-dimethylaminopyridine (22g, 180mmol) was carefully added in small increments (gas evolved). After stirring for 4 hours at room temperature, the precipitate was filtered, the reaction mixture was concentrated to

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half volume, and the precipitate was filtered again. The same procedure was repeated once more and the precipitates were combined and washed with methanol to give 26.4g (51mmol, 29％ yield) of I2BocCz. I2BocCz; 1H NMR (400 MHz, CDCl3, 22.2oC, ppm): δ 8.13 (2.0H, d, J = 1.5 Hz), 7.99 (2.0H, d, J = 8.8 Hz), 7.71 (2.0H, dd, J = 8.8, 1.5 Hz), 1.74 (9.0H, s). 13C NMR (100 MHz, CDCl3, 23.6oC, ppm): δ150.35, 137.71, 136.08, 128.52, 126.43, 118.09, 86.77, 84.75, 28.30. Anal. Calcd for C17H15I2NO2: C, 39.33; H, 2.91; N, 2.70. Found: C, 39.04; H, 2.90; N, 2.59. CzG2on (General procedure for N-arylation reaction, and Boc cleavage). Carbazole (7.03g, 42mmol), I2BocCz (10.0g, 19.3mmol), CuI (371mg, 1.95mmol), and K3PO4 (31.9g, 150mmol) were added to a 3-necked flask, and then (±)-trans-1,2-cyclohexanediamine (347μl, 2.89mmol) and dioxane (120ml) were added under a nitrogen atmosphere. After stirring for 24h at 110℃, the reaction mixture was cooled to room temperature, diluted with toluene (1000ml), filtered through silica gel, and the filtrate was concentrated. This mixture was dissolved in toluene (180ml), and a mixture of trifluoroacetic acid (TFA, 240ml), water (60ml), and anisole (30ml) was added. It was stirred for 48h at room temperature and more TFA (150ml) was again added. After stirring for another 24h, the reaction mixture was neutralized with aqueous potassium carbonate, the organic layer was separated, washed with brine, and filtered through silica gel. The product was isolated by silica gel column chromatography (toluene: hexane = 3: 2 → 2: 1). Yield: 58% (5.55g, 11.1mmol, 2 steps). The identification of CzG2on was done by 1H-NMR and MALDI-TOF-MS, and matched recent reports. See reference 20a in the text. CzG3on. As per the general procedure for the N-arylation reaction and Boc cleavage, CzG2on (2466mg, 4.96mmol), I2BocCz (1190mg, 2.29mmol), CuI (45.3mg, 0.24mmol), K3PO4 (4985mg, 23.5mmol), (±)-trans-1,2-cyclohexanediamine (41μl, 0.37mmol), and dioxane (15ml) were heated in an oil bath at 110℃ for 24h. After a 72h deprotection with toluene (60ml), TFA (80ml + 40ml after 48h), water (20ml), and anisole (10ml), the product was isolated by silica gel column chromatography (toluene: hexane = 2: 1 → 10: 1). Yield: 75% (1983mg, 1.71mmol, 2 steps). CzG3on; 1H NMR (400MHz, CDCl3, 20.0 oC, ppm, 10.3mg/ml): δ 8.52 (1.0H, s), 8.43 (2.0H, s), 8.29 (4.0H, t, J = 2.0 Hz), 8.17-8.14 (8.0H, m), 7.82-7.79 (4.0H, m), 7.63-7.60 (8.0H, m), 7.40-7.39 (16.0H, m), 7.29-7.27 (8.0H, m).

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C NMR (100 MHz, CDCl3, 20.1oC, ppm, 10.3mg/ml): δ

141.59, 141.40, 139.47, 130.00, 129.25, 126.08, 125.71, 124.02, 123.54, 122.94, 120.13, 119.82, 119.63, S4

119.51, 112.36, 111.09, 109.54. MALDI TOF-MS: Calcd: 1157.4 ([M]+), Found: 1157.4. Anal. Calcd for C84H51N7: C, 87.10; H, 4.44; N, 8.46. Found: C, 86.83; H, 4.58; N, 8.34. CzG4on. As per the general procedure for the N-arylation reaction and Boc cleavage, CzG3on (1493mg, 1.29mmol), I2BocCz (302mg, 0.58mmol), CuI (11.2mg, 0.059mmol), K3PO4 (1387mg, 6.53mmol), (±)-trans-1,2-cyclohexanediamine (10.6μl, 0.088mmol), and dioxane (5ml) were heated in an oil bath at 110℃ for 24h. After a 72h deprotection with toluene (30ml), TFA (40ml + 20ml after 48h), water (10ml), and anisole (5ml), the product was isolated by silica gel column chromatography (toluene: hexane = 4: 1 → 10: 1 → 10: 0) and then purified using preparative GPC (chloroform eluent). Yield: 47% (685mg, 0.28mmol, 2 steps). CzG4on; 1H NMR (400MHz, CDCl3, 21.3 oC, ppm, 32.7mg/ml): δ 8.54 (4.0H, d, J = 2.0 Hz), 8.52 (2.0H, d, J = 2.0 Hz), 8.27 (8.0H, d, J = 2.4 Hz), 8.12 (16.0H, t, J = 3.2 Hz), 7.89-7.73 (13.0H, m), 7.64-7.60 (16.0H, m), 7.36-7.34 (32.0H, br m), 7.23-7.23 (16.0H, br m).

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C NMR (100 MHz, CDCl3, 21.4oC, ppm, 32.7mg/ml): δ

141.99, 141.67, 141.49, 139.77, 130.14, 129.64, 129.16, 126.21, 125.79, 124.15, 123.81, 123.67, 123.03, 120.21, 119.97, 119.77, 119.61, 112.74, 111.66, 111.13, 109.58. MALDI TOF-MS: Calcd: 2478.9 ([M]+), Found: 2476.4. Anal. Calcd for C180H107N15: C, 87.18; H, 4.35; N, 8.47. Found: C, 86.38; H, 4.43; N, 8.15.

Figure S1. Elution curves of SEC measurements of CzGnon by an RI detector.

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2-2. Benzene substituted carbazole dendrons (GnPh)

Reagents & Conditions: (a) CuI, trans-1,2-cyclohexanediamine, K3PO4, dioxane, 110℃, 24h

G2Ph. As per the general procedure for the N-arylation reaction, CzG2on (248mg, 0.50mmol), iodobenzene (123mg,

0.60mmol),

CuI

(9.56mg,

0.050mmol),

K3PO4

(253mg,

1.19mmol),

(±)-trans-1,2-

cyclohexanediamine (9.0μl, 0.075mmol), and dioxane (2ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 2: 1). Yield: 40% (114mg, 0.20mmol).

G2Ph; 1H NMR (400 MHz, CDCl3, 20.1 oC, ppm): δ 8.26 (2.0H, s), 8.14 (4.0H, d, J = 7.8 Hz),

7.65-7.58 (9.0H, m), 7.38 (8.0H, d, J = 3.9 Hz), 7.29-7.23 (4.0H, m).

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C NMR (100 MHz, CDCl3, 20.4 oC,

ppm): δ 141.64, 140.56, 136.99, 130.22, 130.14, 128.13, 127.11, 126.14, 125.80, 123.82, 123.05, 120.21, 119.60, 111.24, 109.62. MALDI TOF-MS: Calcd: 573.2 ([M]+), Found: 574.1. Anal. Calcd for C42H27N3: C, 87.93; H, 4.74; N, 7.32. Found: C, 87.84; H, 4.81; N, 7.21. S6

G3Ph. As per the general procedure for the N-arylation reaction, CzG3on (271mg, 0.23mmol), iodobenzene (57.1mg,

0.28mmol),

CuI

(4.45mg,

0.023mmol),

K3PO4

(2172mg,

10.2mmol),

(±)-trans-1,2-


G3Ph; 1H NMR (400 MHz, CDCl3, 20.2oC, ppm): δ 8.51 (2.0H, s), 8.29 (4.0H, d, J = 2.0 Hz),

8.12 (8.0H, d, J = 7.8 Hz), 7.78-7.74 (8.0H, m), 7.67-7.58 (9.0H, m), 7.38-7.36 (16.0H, m), 7.26-7.22 (8.0H, m). 13

C NMR (100 MHz, CDCl3, 20.8 oC, ppm):

δ141.68, 141.49, 141.10, 136.76, 130.32, 130.12, 129.70, 128.48,

127.19, 126.22, 125.80, 123.97, 123.67, 123.03, 120.23, 120.19, 119.87, 119.78, 119.72, 119.59, 111.76, 111.19, 109.62. MALDI TOF-MS: Calcd: 1233.5 ([M]+), Found: 1233.7. Anal. Calcd for C90H55N7: C, 87.57; H, 4.49; N, 7.94. Found: C, 87.17; H, 4.61; N, 7.83. G4Ph. As per the general procedure for the N-arylation reaction, CzG4on (276mg, 0.11mmol), iodobenzene (222mg,

1.09mmol),

CuI

(4.94mg,

0.026mmol),

K3PO4

(153mg,

0.72mmol),

(±)-trans-1,2-


G4Ph; 1H NMR (400 MHz, CDCl3, 22.0 oC, ppm): δ 8.66 (2.0H, s), 8.54 (4.0H, s), 8.27 (8.0H,

d, J = 1.5 Hz), 8.09 (16.0H, d, J = 7.8 Hz), 7.87-7.82 (17.0H, m), 7.65 (8.0H, d, J = 8.8 Hz), 7.57 (8.0H, d, J = 8.3 Hz), 7.36-7.33 (32.0H, br m), 7.22-7.21 (16.0H, br m).

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C NMR (100 MHz, CDCl3, 20.8 oC, ppm): δ

141.99, 141.65, 141.49, 141.36, 136.67, 130.46, 130.13, 129.66, 129.53, 128.72, 127.25, 126.42, 126.33, 126.20, 125.76, 124.05, 123.83, 123.66, 123.01, 120.19, 120.00, 119.77, 119.58, 112.07, 111.66, 111.13, 109.56. MALDI TOF-MS: Calcd: 2555.9 ([M]+), Found: 2554.2. Anal. Calcd for C186H111N15: C, 87.40; H, 4.38; N, 8.22. Found: C, 87.03; H, 4.47; N, 7.89.

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Figure S2. Elution curves of SEC measurements of GnPh by an RI detector.

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2-3. Benzophenone and phenylazomethine substituted carbazole dendrons (GnB, and GnA)

reagents & conditions (a) CuI, K3PO4, trans-1,2-cyclohexanediamine, dioxane, 110℃, 24h (b) Aniline, TiCl4, DABCO, PhCl, 125℃, few hours.

4,4’-Diiodobenzophenone (general procedure for the conversion reaction of Br to I). To a mixture of 4,4’-dibromobenzophenone (2039mg, 6.00mmol), CuI (129, 0.68mmol), and NaI (3664mg, 24.4mmol), trans-N,N′-dimethylcyclohexane-1,2-diamine (192μl, 1.28mmol), and dioxane (10ml) were added under a nitrogen atmosphere. The mixture was heated to 110℃ and stirred for 24h. After cooling to room temperature, the reaction mixture was diluted with toluene (1500ml), filtered through silica gel, and the filtrate was concentrated. The conversion of Br to I was determined by NMR integration to be 91%, and the yield was quantitative. This mixture was used as 4,4’-diiodobenzophenone in the following reactions. 1H NMR of 4,4’-diiodobenzophenone (270MHz, CDCl3, 18.5oC, ppm,): δ 7.86 (4.0H, d, J = 8.6 Hz), 7.49 (4.0H, d, J = 8.4 Hz). G1B. As per the general procedure for the N-arylation reaction, carbazole (1417mg, 8.47mmol), 4-4’-diiodobenzophenone (1653mg, 3.8mmol), CuI (8.00mg, 0.042mmol), K3PO4 (4162mg, 19.6mmol), (±)-trans-1,2-cyclohexanediamine (46μl, 0.38mmol), and dioxane (15ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (hexane: chloroform = 3: 2). Yield: S9

80% (1556mg, 3.0mmol). The identification of G1B was done by 1H-NMR and MALDI-TOF-MS, and matched recent reports. See reference 22a in the text. G2B. As per the general procedure for the N-arylation reaction, CzG2on (1193mg, 2.40mmol), 4-4’-diiodobenzophenone (426mg, 0.98mmol), CuI (9.57mg, 0.050mmol), K3PO4 (1864mg, 8.78mmol), (±)-trans-1,2-cyclohexanediamine (12μl, 0.10mmol), and dioxane (15ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 2: 1). Yield: 77% (884mg, 0.75mmol). The identification of G2B was done by 1H-NMR and MALDI-TOF-MS, and matched recent reports. See reference 22a in the text. G3B. As per the general procedure for the N-arylation reaction, CzG3on (995mg, 0.86mmol), 4-4’-diiodobenzophenone (154mg, 0.36mmol), CuI (14.2mg, 0.075mmol), K3PO4 (804mg, 3.79mmol), (±)-trans-1,2-cyclohexanediamine (13μl, 0.11mmol), and dioxane (7.5ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 2: 1 → 10: 1), and then purified using preparative GPC (chloroform eluent). Yield: 85% (753mg, 0.030mmol). G3B; 1H NMR (400 MHz, CDCl3, 22.8oC, ppm): δ 8.57 (4.0H, d, J = 2.0 Hz), 8.41 (4.0H, d, J = 8.3 Hz), 8.32 (8.0H, d, J = 2.0 Hz), 8.14 (16.0H, d, J = 7.8 Hz), 8.07 (4.0H, d, J = 8.3 Hz), 7.95 (4.0H, d, J = 8.8 Hz), 7.89 (4.0H, dd, J = 8.8, 2.0 Hz), 7.68 (8.0H, d, J = 8.3 Hz), 7.64-7.60 (8.0H, m), 7.39-7.37 (32.0H, m), 7.28-7.25 (16.0H, m). 13C NMR (100 MHz, CDCl3, 24.0oC, ppm): δ194.05, 141.79, 141.49, 141.17, 140.57, 136.73, 132.34, 130.61, 130.39, 126.92, 126.70, 126.37, 125.89, 124.71, 123.86, 123.15, 120.32, 120.20, 119.92, 119.72, 111.78, 111.15, 109.63. MALDI TOF-MS: Calcd: 2494.9 ([M+H]+), Found: 2494.4. Anal. Calcd for C181H108N14O: C, 87.14; H, 4.36; N, 7.86. Found: C, 86.80; H, 4.35; N, 8.11. G4B. As per the general procedure for the N-arylation reaction, CzG4on (800mg, 0.32mmol), 4-4’-diiodobenzophenone (64mg, 0.15mmol), CuI (7.0mg, 0.037mmol), K3PO4 (409mg, 1.93mmol), (±)-trans-1,2-cyclohexanediamine (5.3μl, 0.044mmol), and dioxane (2ml) were heated in an oil bath at 110℃ for 24h. CuI (7.0mg, 0.037mmol), (±)-trans-1,2- cyclohexanediamine (5.3μl, 0.044mmol), and dioxane (2ml) were then added to the reaction mixture, and stirred for another 33h. The product was isolated by silica gel column chromatography (toluene: hexane = 10: 1), and then purified using preparative GPC (chloroform eluent). Yield: 32% (243mg, 0.047mmol). G4B; 1H NMR (400 MHz, CDCl3, 21.9oC, ppm): δ 8.71 (4.0H, d, J = S10

1.5 Hz), 8.56 (8.0H, s), 8.49 (4.0H, d, J = 8.3 Hz), 8.28 (16.0H, d, J = 2.0 Hz), 8.15 (4.0H, d, J = 8.8 Hz), 8.09 (32.0H, d, J = 7.8 Hz), 8.05 (4.0H, d, J = 8.8 Hz), 7.99 (4.0H, d, J = 5.1 Hz), 7.83 (16.0H, s), 7.64 (16.0H, d, J = 8.8 Hz), 7.57-7.56 (16.0H, br m), 7.33-7.32 (64.0H, br m), 7.22-7.20 (32.0H, br m).

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C NMR (100 MHz,

CDCl3, 23.2oC, ppm): δ 193.91, 141.97, 141.73, 141.54, 141.10, 140.82, 136.88, 132.45, 130.45, 130.28, 129.94, 127.05, 126.86, 126.47, 126.29, 125.84, 124.77, 124.02, 123.77, 123.36, 123.10, 120.28, 119.88, 119.68, 112.03, 111.58, 111.10, 109.57. MALDI TOF-MS: Calcd: 5138.8 ([M+H]+), Found: 5136.1. Anal. Calcd for C373H220N30O: C, 87.19; H, 4.32; N, 8.18. Found: C, 86.23; H, 4.36; N, 7.81.

Figure S3. Elution curves of SEC measurements of GnB by an RI detector. G1A (general procedure for dehydration reaction using TiCl4). G1B (259mg, 0.51mmol), aniline (186mg, 1.99mmol), and 1,4-diazabicyclo[2.2.2]octane (DABCO, 598mg, 4.95mmol) were dissolved in chlorobenzene (20mL) and heated to 75 °C. TiCl4 (194mg, 1.02mmol) dissolved in 5mL of chlorobenzene was dropwise added, and the addition funnel was then rinsed with 5mL of chlorobenzene. The mixture was heated to 125 °C

S11

and stirred for 3 h under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and stirred overnight in air and then filtered through Celite. The filtrate was concentrated, and the product was isolated by silica gel (neutral) column chromatography (toluene: hexane = 1: 1 with 2% Et3N). Yield: 79% (234 mg, 0.40mmol). G1A; 1H NMR (400 MHz, CDCl3, 21.4oC, ppm): δ 8.16 (2.0H, s), 8.13 (4.0H, dd, J = 8.3, 2.4 Hz), 7.71 (2.0H, d, J = 8.3 Hz), 7.53 (4.0H, t, J = 7.1 Hz), 7.44-7.39 (8.0H, m), 7.33-7.23 (6.0H, m), 7.03 (1.0H, t, J = 7.6 Hz), 6.85 (2.0H, d, J = 7.8 Hz). 13C NMR (100 MHz, CDCl3, 24.2oC, ppm): δ 166.42, 150.84, 140.37, 140.15, 138.02, 137.99, 134.73, 131.11, 130.84, 128.63, 126.46, 126.40, 126.04, 125.96, 123.65, 123.62, 123.49, 120.99, 120.34, 120.28, 120.20, 109.78, 109.58. MALDI TOF-MS: Calcd: 588.2 ([M+H]+), Found: 589.4. Anal. Calcd for C43H29N3: C, 87.88; H, 4.97; N, 7.15. Found: C, 87.63; H, 5.15; N, 7.01. G2A. As per the general procedure for the dehydration reaction, G2B (295mg, 0.25mmol), aniline (93mg, 1.00mmol), and DABCO (569mg, 5.07mmol) were dissolved in chlorobenzene (20mL). TiCl4 (194mg, 1.02mmol) was added, and the mixture was stirred for 3h at 125 °C. The product was isolated by silica gel (neutral) column chromatography (toluene: hexane = 2: 1 with 2% Et3N). Yield: 69% (215mg, 0.17mmol). G2A: 1H NMR (400 MHz, CDCl3, 23.3oC, ppm): δ 8.28 (4.0H, dd, J = 6.3, 4.4 Hz), 8.25 (2.0H, s), 8.14 (8.0H, d, J = 7.8 Hz), 7.88 (2.0H, d, J = 8.3 Hz), 7.77 (2.0H, d, J = 8.3 Hz), 7.70 (2.0H, d, J = 8.3 Hz), 7.65-7.56 (8.0H, m), 7.39-7.37 (16.0H, br m), 7.31-7.23 (10.0H, br m), 7.07-7.04 (1.0H, m), 6.90 (2.0H, d, J = 8.3 Hz).

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C

NMR (100 MHz, CDCl3 , 23.0oC, ppm) : δ165.95, 150.68, 141.59, 140.14, 140.12, 139.56, 138.64, 137.49, 135.46, 131.42, 131.15, 130.72, 130.65, 128.73, 126.65, 126.62, 126.34, 126.29, 125.84, 124.25, 124.12, 123.88, 123.11, 120.93, 120.26, 119.77, 119.70, 111.27, 111.09, 109.57, 109.54. MALDI-TOF-MS: Calcd: 1248.5 ([M+H]+), Found: 1247.9. Anal. Calcd for C91H57N7: C, 87.54; H, 4.60; N, 7.85. Found: C, 87.22; H, 4.58; N, 7.77. G3A. As per the general procedure for the dehydration reaction, G3B (248mg, 0.10mmol), aniline (93mg, 1.00mmol), and DABCO (593mg, 5.29mmol) were dissolved in chlorobenzene (20mL). TiCl4 (173mg, 0.91mmol) was added, and the mixture was stirred for 3h at 125 °C. The product was isolated by silica gel (neutral) column chromatography (toluene: hexane = 10: 1 with 2% Et3N). Yield: 86% (221mg, 0.086mmol). G3A: 1H NMR (400MHz, CDCl3, 20.1oC, ppm): δ 8.53 (4.0H, d, J = 10.7 Hz), 8.38 (2.0H, d, J = 8.3 Hz), 8.30 (8.0H, s), 8.12 (16.0H, d, J = 7.8 Hz), 7.99 (2.0H, d, J = 8.3 Hz), 7.93 (2.0H, d, J = 8.8 Hz), 7.87-7.76 (8.0H, m), S12

7.67-7.61 (20.0H, m), 7.39-7.35 (32.0H, m), 7.26-7.23 (16.0H, m), 7.12 (1.0H, t, J = 7.6 Hz), 6.97 (2.0H, d, J = 7.8 Hz). 13C NMR (100 MHz, CDCl3, 21.3oC, ppm): δ165.82, 150.64, 141.67, 141.42, 141.40, 140.69, 140.64, 139.37, 138.95, 137.33, 135.77, 131.60, 131.32, 130.23, 130.16, 128.81, 126.79, 126.50, 126.26, 125.80, 124.40, 124.29, 124.02, 123.73, 123.05, 120.96, 120.23, 120.04, 119.82, 119.63, 111.74, 111.57, 111.09, 109.57. MALDI-TOF-MS: Calcd: 2569.9 ([M+H]+), Found: 2569.2. Anal. Calcd for C187H113N15: C, 87.39; H, 4.43; N, 8.18. Found: C, 87.02; H, 4.48; N, 7.99. G4A. As per the general procedure for the dehydration reaction, G4B (183mg, 0.036mmol), aniline (33mg, 0.35mmol), and DABCO (426mg, 3.80mmol) were dissolved in chlorobenzene (10mL). TiCl4 (132mg, 0.696mmol) was added, and the mixture was stirred for 3h at 125 °C. The product was isolated by silica gel (neutral) column chromatography (toluene: hexane = 1: 4 with 2% Et3N). Yield: 84% (157mg, 0.030mmol). G4A: 1H NMR (400 MHz, CDCl3, 19.4oC, ppm): δ 8.69 (4.0H, d, J = 10.7 Hz), 8.55 (8.0H, s), 8.47 (2.0H, d, J = 7.8 Hz), 8.28 (16.0H, s), 8.09 (32.0H, d, J = 7.8 Hz), 8.04 (4.0H, d, J = 8.8 Hz), 7.97 (4.0H, t, J = 7.3 Hz), 7.90 (4.0H, t, J = 9.3 Hz), 7.82 (16.0H, d, J = 5.4 Hz), 7.78 (4.0H, d, J = 8.8 Hz), 7.64 (16.0H, dd, J = 8.5, 1.7 Hz), 7.56 (16.0H, d, J = 8.8 Hz), 7.39-7.31 (64.0H, br m), 7.22-7.21 (34.0H, br m), 7.00 (2.0H, d, J = 7.8 Hz). 13

C NMR (100 MHz, CDCl3, 19.8oC, ppm): δ 165.69, 150.60, 141.89, 141.62, 141.43, 140.97, 140.89, 139.33,

139.11, 137.30, 135.91, 131.73, 131.47, 130.17, 130.07, 130.03, 129.79, 128.86, 126.89, 126.65, 126.36, 126.21, 125.76, 124.48, 124.38, 123.90, 123.68, 123.02, 122.72, 120.97, 120.22, 119.79, 119.61, 111.81, 111.54, 111.05, 109.52 . MALDI-TOF-MS: Calcd: 5213.9 ([M+H]+), Found: 5212.0. Anal. Calcd for C379H225N31: C, 87.32; H, 4.35; N, 8.33. Found: C, 86.40; H, 4.42; N, 8.07.

S13

Figure S4. Elution curves of SEC measurements of GnA by an RI detector.

S14

2-4. Ferrocene substituted carbazole dendrons (GnFc)

reagents & conditions (a) NaNO2, H2SO4, water, 0℃ (b) Urea, AcONa・3H2O, AcOH, dichloroethane, 0℃→R.T., over night. (c) CuI,NaI,rac-trans-N,N'-Dimethyl-1,2-cyclohexanediamine, dioxane, 110℃, 24h (d) CuI, K3PO4, trans-1,2 cyclohexanediamine, dioxane, 110℃, 24h.

4-bromophenylferrocene (FcPhBr) and phenylferrocene (G0Fc). The FcPhBr and FcPhG0 were obtained according to the literature methods. See reference 27 in the main text. 4-iodophenylferrocene (FcPhI). As per the general procedure for the conversion reaction of Br to I, FcPhBr (672mg, 1.97mmol), NaI (690mg, 4.60mmol), CuI (19.0mg, 0.100mmol), trans-N,N′-dimethylcyclohexane1,2-diamine (30μl, 0.200mmol), and dioxane (2ml) were heated to 110℃ and stirred for 24h. The conversion of Br to I was determined by NMR integration to be 88%, and the yield was quantitative. This mixture was used as FcPhI in the following reactions. 1H NMR of FcPhI; 1H NMR (270 MHz, CDCl3, 21.4oC, ppm): δ 7.58 (2.0H, d, J = 8.8 Hz), 7.20 (2.0H, d, J = 8.8 Hz), 4.60 (2.0H, t, J = 1.7 Hz), 4.32 (2.0H, t, J = 2.0 Hz),

S15

4.03 (5.0H, s). G1Fc. As per the general procedure for the N-arylation reaction, carbazole (155mg, 0.93mmol), FcPhI (285mg,

0.73mmol),

CuI

(14.8mg,

0.078mmol),

K3PO4

(598mg,

2.82mmol),

(±)-trans-1,2-

cyclohexanediamine (13.9μl, 0.12mmol), and dioxane (3ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 2: 3). Yield: 77% (242mg, 0.57mmol). G1Fc; 1H NMR (400 MHz, CDCl3, 23.1oC, ppm): δ 8.15 (2.0H, d, J = 7.8 Hz), 7.67 (2.0H, d, J = 8.3 Hz), 7.48-7.40 (6.0H, m), 7.30-7.26 (2.0H, m), 4.71 (2.0H, s), 4.38 (2.0H, s), 4.12 (5.0H, s). 13C NMR (100 MHz, CDCl3, 24.1oC, ppm): δ 140.89, 138.81, 135.26, 127.30, 126.97, 125.87, 123.30, 120.27, 119.81, 109.85, 84.56, 69.72, 69.25, 66.66. MALDI TOF-MS: Calcd: 427.1 ([M]+), Found: 428.4. G2Fc. As per the general procedure for the N-arylation reaction, CzG2on (226mg, 0.45mmol), FcPhI (147mg, 0.38mmol), CuI (8.0mg, 0.042mmol), K3PO4 (285mg, 1.34mmol), (±)-trans-1,2-cyclohexanediamine (7.0μl, 0.058mmol), and dioxane (2ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 2: 3). Yield: 47% (137mg, 0.18mmol). G2Fc; 1H NMR (400 MHz, CDCl3, 22.9oC, ppm): δ 8.27 (2.0H, d, J = 1.5 Hz), 8.15 (4.0H, d, J = 7.8 Hz), 7.78 (2.0H, dd, J = 6.8, 2.0 Hz), 7.69 (2.0H, d, J = 8.8 Hz), 7.63-7.61 (4.0H, m), 7.39 (8.0H, d, J = 3.4 Hz), 7.29-7.25 (4.0H, m), 4.76 (2.0H, t, J = 1.7 Hz), 4.41 (2.0H, t, J = 2.0 Hz), 4.15 (5.0H, s). 13C NMR (100 MHz, CDCl3, 24.1oC, ppm): δ 141.78, 140.71, 139.88, 134.59, 130.28, 127.63, 127.08, 126.22, 125.89, 123.90, 123.15, 120.29, 119.70, 119.67, 111.42, 109.70, 84.20, 69.77, 69.44, 66.76. MALDI TOF-MS: Calcd: 757.2 ([M]+), Found: 757.8. G3Fc. As per the general procedure for the N-arylation reaction, CzG3on (342mg, 0.30mmol), FcPhI (95mg, 0.25mmol), CuI (5.0mg, 0.026mmol), K3PO4 (164mg, 0.77mmol), (±)-trans-1,2-cyclohexanediamine (4.7μl, 0.039mmol), and dioxane (2ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 1: 1), and then purified using preparative GPC (chloroform eluent). Yield: 54% (196mg, 0.14mmol). G3Fc; 1H NMR (400 MHz, CDCl3, 23.2oC, ppm): δ 8.54 (2.0H, t, J = 1.2 Hz), 8.32 (4.0H, d, J = 1.5 Hz), 8.16 (8.0H, d, J = 7.8 Hz), 7.84 (4.0H, d, J = 1.0 Hz), 7.82 (2.0H, s), 7.70-7.68 (6.0H, m), 7.63 (4.0H, dd, J = 8.5, 2,2 Hz), 7.43-7.37 (16.0H, m), 7.30-7.26 (8.0H, m), 4.79 (2.0H, t, J = 2.0 Hz), 4.45 (2.0H, t, J = 1.7 Hz), 4.18 (5.0H, s). 13C NMR (100 MHz, CDCl3, 24.1oC, ppm): δ 141.81, 141.61, 141.23, 140.33, 134.27, 130.23, 129.75, 127.74, 127.14, 126.30, 125.87 124.04, 123.75, 123.13, 120.28, S16

119.91, 119.83, 119.66, 111.93, 111.25, 109.68, 84.01, 69.79, 69.55, 66.79. MALDI TOF-MS: Calcd: 1418.5 ([M]+), Found: 1418.5. G4Fc. As per the general procedure for the N-arylation reaction, CzG4on (300mg, 0.12mmol), FcPhI (56mg, 0.14mmol), CuI (4.9mg, 0.026mmol), K3PO4 (93mg, 0.026mmol), (±)-trans-1,2-cyclohexanediamine (4.4μl, 0.037mmol), and dioxane (2ml) were heated in an oil bath at 110℃ for 24h. The product was isolated by silica gel column chromatography (toluene: hexane = 2: 1), and then purified using preparative GPC (chloroform eluent). Yield: 34% (112mg, 0.041mmol). G4Fc; 1H NMR (400 MHz, CDCl3, 22.7oC, ppm): δ 8.69 (2.0H, s), 8.59 (4.0H, s), 8.31 (8.0H, d, J = 2.0 Hz), 8.14 (16.0H, d, J = 7.8 Hz), 7.95 (4.0H, s), 7.89 (2.0H, t, J = 5.4 Hz), 7.86 (8.0H, d, J = 1.0 Hz), 7.77 (2.0H, d, J = 8.8 Hz), 7.69 (8.0H, d, J = 8.3 Hz), 7.61 (8.0H, d, J = 8.8 Hz), 7.38 (32.0H, s), 7.26 (16.0H, d, J = 6.3 Hz), 4.83 (2.0H, t, J = 1.7 Hz), 4.48 (2.0H, t, J = 1.7 Hz), 4.21 (4.0H, s). 13C NMR (100 MHz, CDCl3, 24.9oC, ppm): δ 142.10, 141.76, 141.59, 141.48, 140.63, 134.11, 130.23, 129.77, 129.56, 127.83, 127.18, 126.40, 126.28, 125.84 124.09, 123.91, 123.73, 123.10, 120.26, 120.08, 119.83, 119.66, 112.23, 111.71, 111.17, 109.62, 83.88, 69.81, 69.64, 66.82. MALDI TOF-MS: Calcd: 2739.9 ([M]+), Found: 2739.1.

Figure S5. Elution curves of SEC measurements of GnFc by an RI detector.

S17

3. Generation-hydrodynamic radius plot

Figure S6. The generation-hydrodynamic radius plot of carbazole dendron derivatives.

4. UV-absorption spectra of G1B

Figure S7. The UV-vis absorption spectra of G1B in several solvents. S18

5. Fluorescence spectra of CzGnon

Figure S8. The fluorescence spectra of CzGnon (1μM THF solution).

6. MOPAC calculated molecular models

Figure S9. A 3D model of CzG3on optimized by the MOPAC (MM2) calculation. The red circle shows the steric overlap.

S19

7. Substituent effect of carbazole

Figure S10. The 1H- and 13C- NMR chemical shifts of benzene, aniline, and 9-phenylcarbazole.

8. RedOx potential of GnFc

Figure S11. The cyclic voltammogram of G0Fc, G1Fc, and G4Fc.

S20

9. UV-vis titration

Figure S12. UV-vis spectral of (a) G0A, (b) G1A, (c) G3A, and (d) G4A during the addition of GaCl3 (solvent is benzene: acetonitrile = 4:1 and the concentrations were 50μM).

S21

10. Assignment of the NMR spectra (GnFc)

Figure S13. The 1H-NMR spectra of GnFc. The arrows are pointing to the 4-position proton of the innermost layer.

S22

Figure S14. The H-H COSY spectrum and the assignment of the 1H-NMR of G2Fc (See the main text for the numbering). The protons that are assigned as “Fc” are the protons of the phenyl ring that is directly bound to the ferrocene ring.

S23


S24


S25

Figure S17. The C-H COSY spectrum and some assignments of the 13C-NMR of G2Fc (See the main text for the numbering). The protons that are assigned as “Fc” are the protons of the phenyl ring that is directly bound to the ferrocene ring.

S26


S27


S28

Figure S20. The HMBC spectrum and some assignments of the 13C-NMR of G3Fc (See the main text for the numbering).

Figure S21. The HMBC spectrum and some assignments of the 13C-NMR of G4Fc (See the main text for the numbering). S29

Figure S22. The complete assignment of the 13C-NMR spectra of GnFc (105-145ppm). S30

Figure S23. The 1H-NMR chemical shifts of each layer (G3Fc, and G2Fc).

S31

Figure S24. The 13C-NMR chemical shifts of each layer (G3Fc, and G2Fc).

S32

11. Molecular models (Gaussian calculation)

Figure S25. (a) A 3D model of G1Ph optimized by Gaussian 03 (DFT calculation with STO-3G as the base function). (b) The LUMO structure, and (c) The HOMO level.

S33


S34


S35

Figure S28. (a) A 3D model of G4Ph optimized by Gaussian 03 (DFT calculation with STO-3G as the base function). (b) The LUMO structure, and (c) The HOMO level. Table S1. The Mulliken charge population of each layer’s nitrogen atom calculated by Gaussian 03 (DFT calculation with STO-3G as the base function).

S36

Gaussian reference (reference 30 in the main text) Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.

S37

12. Crystal Structure Determination

Figure S29. ORTEP diagrams of G1B with 50% probability. The bond radius is 0.06 Å, and the solvent molecule is removed. Crystal data of G1B. C38H25Cl3N2O, M = 631.99, orthorhombic, space group P n a 21, a =8.790 Å, b = 45.709 Å, c = 7.605(10) Å, α = 90.00o, β = 90.00o, γ = 90.00 o, U = 3055.65 Å3, Z = 4, Dcalc = 1.374 g/cm3, μ = 2.985 mm-1, crystal size 0.5 x 0.07 x 0.05 mm, 2951 reflections measured, S = 0.918, R = 0.037, and Rw = 0.035. Yellow block crystals of G1B were obtained by the slow evaporation of the G1B chloroform solution. A suitable crystal was mounted in a cryoloop. The intensity data were collected at 223K by a Rigaku RAXIS-RAPID diffractometer with graphite monochromatized Cu Kα radiation (λ = 1.5419 Å). The structure was solved by a direct method (SIR92) on a Dell workstation with the program system CrystalStructure. The structure was refined on F2 by full-matrix least square methods using 1182 reflections within I>2.0σ(I) and the final R value was 0.037. The atomic parameters are listed in the CIF file.

Figure S30. ORTEP diagrams of G2B with 50% probability. The bond radius is 0.06 Å, and the solvent molecules are removed. Crystal data of G2B. C109H52N6O, M = 1461.65, triclinic, space group P -1, a = 14.008 Å, b = 17.580 Å, c = 18.722 Å, α = 76.26o, β = 74.55o, γ = 74.56 o, U = 4213.9 Å3, Z = 2, Dcalc = 1.152 g/cm3, μ = 0.531 mm-1, crystal size 0.5 x 0.2 x 0.05 mm, 14333 reflections measured, S = 1.036, R = 0.097, and Rw = 0.297. Yellow chip crystals of G2B were obtained by the slow diffusion of hexane vapor into the THF solution of G2B. A suitable crystal was mounted in a cryoloop. The intensity data were collected at 223K by a Rigaku S38

RAXIS-RAPID diffractometer with graphite monochromatized Cu Kα radiation (λ = 1.5419 Å). The structure was solved by a direct method (SIR92) on a Dell workstation with the program system CrystalStructure. The structure was refined on F2 by full-matrix least square methods using 3794 reflections within I>2.0σ(I) and the final R value was 0.097. The atomic parameters are listed in the CIF file.

Figure S31. ORTEP diagrams of G1Fc with 50% probability. The bond radius is 0.06 Å. Crystal data of G1Fc. C28H21FeN, M = 427.33, monoclinic, space group P 1 21 1, a = 8.127 Å, b = 12.837 Å, c = 9.775 Å, α = 90.00o, β = 99.49o, γ = 90.00o, U = 1005.8 Å3, Z = 2, Dcalc = 1.411 g/cm3, μ = 0.764 mm-1, crystal size 0.1 x 0.1 x 0.1 mm, 4575 reflections measured, S = 0.617, R = 0.027, and Rw = 0.072. Orange chip crystals of G1Fc were obtained by the slow diffusion of methanol vapor into the chloroform solution of G1Fc. A suitable crystal was mounted in a cryoloop. The intensity data were collected at 223K by a Rigaku RAXIS-RAPID diffractometer with graphite monochromatized Mo Kα radiation (λ = 0.71069 Å). The structure was solved by a direct method (SIR92) on a Dell workstation with the program system CrystalStructure. The structure was refined on F2 by full-matrix least square methods using 4080 reflections within I>2.0σ(I) and the final R value was 0.027. The atomic parameters are listed in the CIF file.

Crystal data of G2Fc. C52H35Cl3FeN3, M = 864.07, monoclinic, space group P 1 21/a 1, a = 10.891 Å, b = 34.733 Å, c = 11.387 Å, α = 90.00o, β = 34.733o, γ = 90.00o, U = 4082.9 Å3, Z = 4, Dcalc = 1.406 g/cm3, μ = 0.607 mm-1, crystal size 0.5 x 0.2 x 0.1 mm, 9330 reflections measured, S = 0.882, R = 0.056, and Rw = 0.139. Orange block crystals of G2Fc were obtained by the slow diffusion of hexane vapor into the chloroform

S39

solution of G2Fc. A suitable crystal was mounted in a cryoloop. The intensity data were collected at 103K by a Rigaku RAXIS-RAPID diffractometer with graphite monochromatized Mo Kα radiation (λ = 0.71069 Å). The structure was solved by a direct method (SIR92) on a Dell workstation with the program system CrystalStructure. The structure was refined on F2 by full-matrix least square methods using 3280 reflections within I>2.0σ(I) and the final R value was 0.056. The atomic parameters are listed in the CIF file.

S40

Dendritic Structure Having a Potential Gradient - ACS Publications

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