Synthesis and Optical Properties of Starburst Carbazoles Based on 9-Phenylcarbazole Core

Guo-Liang Feng; Shun-Jun Ji; Wen-Yong Lai; Wei Huang

doi:10.1055/s-2006-950266

LETTER

Synthesis and Optical Properties of Starburst Carbazoles Based on 9-Phenylcarbazole Core

Guo-Liang Feng^a, Shun-Jun Ji*^a, Wen-Yong Lai^b, Wei Huang*^b,c,d
^a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering, Suzhou (Soochow) University, Hengyi Road, Suzhou Industrial Park, Suzhou 215123, P. R. of China
Fax: +86(512)65880089; e-Mail: shunjun@suda.edu.cn;
^b Institute of Advanced Materials (IAM), Fudan University, 220 Handan Road, Shanghai 200433, P. R. of China
^c Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications, 66 XinMoFan Road, Nanjing 210003, P. R. of China
^d Faculty of Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Republic of Singapore
Fax: +86(25)83492349; e-Mail: wei-huang@njupt.edu.cn;

Abstract

Alle Artikel dieser Rubrik

Abstract

New well-defined starburst carbazole derivatives, which contain N-phenylcarbazole as the central core joining 9-hexylcarbazole or 9-phenylcarbazole as arms, are presented. All these compounds were obtained via Suzuki cross-coupling in moderate yields. Their structures were confirmed by ¹H NMR, MALDI-TOF mass spectrometry and elementary analysis. Moreover, the fluorescence spectra showed that these compounds exhibited good blue fluorescence with the maximum wavelengths ranging from 410 nm to 430 nm.

Key words

carbazole - starburst - boronic acids - Suzuki cross-coupling - fluorescence

Volltext

Referenzen

References and Notes

1a Baba A. Onishi K. Knoll W. Advincula RC. J. Phys. Chem. B 2004, 108: 18949

1b Kundu P. Justin Thomas KR. Lin JT. Tao YT. Chien CH. Adv. Funct. Mater. 2003, 13: 445

2a Kuwabara Y. Ogawa H. Inada H. Noma N. Shirota Y. Adv. Mater. (Weinheim, Ger.) 1994, 6: 677

2b Koene BE. Loy DE. Thompson ME. Chem. Mater. 1998, 10: 2235

2c Brien DF. Burrows PE. Forrest SR. Koene BE. Loy DE. Thompson ME. Adv. Mater. (Weinheim, Ger.) 1998, 10: 1108

3a Wakim S. Bouchard J. Simard M. Drolet N. Tao Y. Leclerc M. Chem. Mater. 2004, 16: 4386

3b Wakim S. Bouchard J. Blouin N. Michaud A. Leclerc M. Org. Lett. 2004, 6: 3413

3c Sonntag M. Kreger K. Hanft D. Strohriegl P. Setayesh S. Leeuw DD. Chem. Mater. 2005, 17: 3031

3d Drolet N. Morin JF. Leclerc N. Wakim S. Tao Y. Leclerc M. Adv. Funct. Mater. 2005, 15: 1671

3e Morin JF. Leclerc M. Ades D. Siove A. Macromol. Rapid Commun. 2005, 26: 761

4a Van D A. Bastiaansen JJAM. Kiggen NMM. Langeveld BMW. Rothe C. Monkman A. Bach I. Stossel P. Brunner K. J. Am. Chem. Soc. 2004, 126: 7718

4b Morin JF. Drolet N. Tao Y. Leclerc M. Chem. Mater. 2004, 16: 4619

4c Justin Thomas KR. Velusamy M. Lin JT. Tao YT. Chien CH. Adv. Funct. Mater. 2004, 14: 387

4d Brunner K. Dijken AV. Borner H. Bastiaansen JJAM. Kiggen NMM. Langeveld BMW. J. Am. Chem. Soc. 2004, 126: 6035

5a Grafe A. Janietz D. Frese T. Wendorff JH. Chem. Mater. 2005, 17: 4979

5b Wu LY. Lin JT. Tao YT. Balasubramaniam E. Su YZ. Ko CW. Chem. Mater. 2001, 13: 2626

5c Li JY. Ma CW. Tang JX. Lee CS. Lee ST. Chem. Mater. 2005, 17: 615

5d Li JY. Liu D. Li YQ. Lee CS. Kwong HL. Lee ST. Chem. Mater. 2005, 17: 1208

5e Feng GL. Lai WY. Ji SJ. Huang W. Tetrahedron Lett. 2006, 47: 7089

5f Lai WY. Zhu R. Fan QL. Hou LT. Cao Y. Huang W. Macromolecules 2006, 39: 3707

6a Zhang Q. Chen JS. Cheng YX. Wang LX. Ma DG. Jing XB. Wang FS. J. Mater. Chem. 2004, 14: 895

6b Justin Thomas KR. Lin JT. Tao YT. Ko CW. J. Am. Chem. Soc. 2001, 123: 9404

7a Tavasli M. Bettington S. Bryce MR. Batsanov AS. Monkman AP. Synthesis 2005, 1619

7b Kanibolotsky AL. Berridge R. Skabara PJ. Perepichka IF. Bradley DDC. Koeberg M. J. Am. Chem. Soc. 2004, 126: 13695

8

Synthesis of Compounds 9 and 11; Typical Procedure
To a solution of the corresponding 3-bromocarbazole derivatives 6 or 7 (10 mmol) in anhyd THF (50 mL) was slowly added n-BuLi (2.5 M in hexane, 4.8 mL, 12.0 mmol) at -78 °C. At this temperature, the reaction mixture was stirred for 1 h before adding triisopropyl borate (3.5 mL, 15.0 mmol). The mixture was allowed to warm to r.t. for
15 h. It was quenched with HCl (2.0 M, 40 mL) and poured into a large amount of water. After extraction with Et₂O (3 × 20 mL), the organic portions were washed with brine before drying over anhyd MgSO₄ and the solvent was evaporated to afford the crude carbazoleboronic acids. The crude product was purified by column chromatography on a silica gel column, eluting with PE and EtOAc (2:1) to afford carbazoleboronic acids, which were then dried in vacuo at 35 °C.
Compound 9: ¹H NMR (400 MHz, CDCl₃): δ = 8.54 (s, 1 H), 8.34-8.38 (m, 2 H), 8.12 (d, J = 8.0 Hz, 1 H), 7.78-7.82 (m, 3 H), 7.60 (s, 1 H), 7.25-7.48 (m, 6 H), 4.34-4.39 (m, 4 H), 1.90-1.98 (m, 4 H), 1.20-1.46 (m, 12 H), 0.88-0.90 (m, 6 H).
Compound 11: ¹H NMR (400 MHz, CDCl₃): δ = 8.60 (s, 1 H), 8.36-8.40 (m, 2 H), 8.07-8.14 (m, 2 H), 7.80-7.86 (m, 2 H), 7.58-7.70 (m, 4 H), 7.28-7.50 (m, 12 H).

9

Synthesis of Starburst Compounds 12-15; General Procedure
To a degassed (N₂) solution of 9-(4-bromophenyl)-3,6-dibromocarbazole (1; 1.0 g, 2.1 mmol) and Pd(PPh₃)₄ catalyst (0.5 g, 0.44 mmol, 7 mol% per C-Br bond) in toluene (30 mL), a solution of carbazoleboronic acid (9.45 mmol) in toluene (20 mL) and a 2 M aq K₂CO₃ solution (13 mL) were added via syringe. The reaction mixture was stirred at 80 °C for 48 h. After cooling, the product was extracted with CH₂Cl₂, washed with water and dried over MgSO₄. The solvent was evaporated to afford the crude mixture. After column chromatography on silica gel, eluting with PE and CH₂Cl₂ (5:1), pure compounds 12-15 were obtained. All the compounds were fully characterized. The analytical and spectral data for these compounds follow:
Compound 12: ¹H NMR (400 MHz, CDCl₃): δ = 8.58 (s, 2 H), 8.46 (d, J = 7.6 Hz, 3 H), 8.21 (d, J = 7.6 Hz, 3 H), 8.01 (d, J = 7.4 Hz, 2 H), 7.78-7.88 (m, 6 H), 7.65 (d, J = 7.4 Hz, 2 H), 7.43-7.56 (m, 7 H), 7.25-7.30 (m, 6 H), 4.32-4.39 (m, 6 H), 1.89-1.92 (m, 6 H), 1.28-1.37 (m, 18 H), 0.87-0.91 (m, 9 H). Anal. Calcd for C₇₂H₇₀N₄: C, 87.23; H, 7.12; N, 5.65. Found: C, 87.30; H, 7.27; N, 5.60. MS (MALDI-TOF): m/z [M⁺] calcd for C₇₂H₇₀N₄: 991; found: 991.
Compound 13: ¹H NMR (400 MHz, CDCl₃): δ = 8.60 (s, 2 H), 8.52 (d, J = 7.6 Hz, 3 H), 8.26 (d, J = 7.6 Hz, 3 H), 8.02 (d, J = 7.4 Hz, 2 H), 7.76-7.86 (m, 6 H), 7.63-7.68 (m, 12 H), 7.44-7.57 (m, 12 H), 7.25-7.36 (m, 6 H). Anal. Calcd for C₇₂H₄₆N₄: C, 89.41; H, 4.79; N, 5.79. Found: C, 89.23; H, 4.82; N, 5.43. MS (MALDI-TOF): m/z [M⁺] calcd for C₇₂H₄₆N₄: 967; found: 967.
Compound 14: ¹H NMR (400 MHz, CDCl₃): δ = 8.63 (s, 2 H), 8.54-8.57 (m, 6 H), 8.45 (s, 3 H), 8.17-8.20 (m, 3 H), 8.04 (d, J = 7.4 Hz, 2 H), 7.79-7.90 (m, 10 H), 7.67 (d, J = 7.4 Hz, 2 H), 7.25-7.49 (m, 15 H), 7.20-7.23 (m, 6 H), 4.3-4.4 (m, 12 H), 1.82-1.97 (m, 12 H), 1.25-1.56 (m, 36 H), 0.84-0.92 (m, 18 H). Anal. Calcd for C₁₂₆H₁₂₇N₇: C, 87.00; H, 7.36; N, 5.64. Found: C, 87.15; H, 7.13; N, 5.80. MS (MALDI-TOF): m/z [M⁺] calcd for C₁₂₆H₁₂₇N₇: 1739; found: 1739.
Compound 15: ¹H NMR (400 MHz, CDCl₃): δ = 8.64 (s, 2 H), 8.58-8.62 (m, 6 H), 8.50 (s, 3 H), 8.22-8.23 (m, 3 H), 8.05 (d, J = 7.4 Hz, 2 H), 7.78-7.88 (m, 12 H), 7.39-7.67 (m, 42 H), 7.24-7.26 (m, 9 H). Anal. Calcd for C₁₂₆H₇₉N₇: C, 89.49; H, 4.71; N, 5.80. Found: C, 89.32; H, 4.49; N, 5.94. MS (MALDI-TOF): m/z [M⁺] calcd for C₁₂₆H₇₉N₇: 1691; found: 1691.