Synthesis and Solvatochromic Behavior of Hexaphenylbenzenes and Indeno[1,2-b]fluorene Derivatives with Hydroxy Groups


Hexakis(4-methoxyphenyl)benzene (HPB-OMe(1)) and hexakis(2,6-dimethyl-4-methoxyphenyl)benzene (HPB-OMe(2)) were synthesized via organometallic complex catalysis. The treatment of HPB-OMe(1) with FeCl3 caused cyclodehydrogenation at two positions to yield an oligophenylene with an indeno[1,2-b]fluorene structure (IF-OMe). Deprotection of the methoxy groups of these compounds was conducted by treatment with BBr3. Deprotonation of the OH groups of HPB-OH(1), HPB-OH(2), and IF-OH through treatment with NaH caused a bathochromic shift in the absorption and photoluminescence (PL) peaks. The bathochromic shift of the deprotonated species increased with the donor number (DN) of the solvents. These observations can be explained as the consequence of intramolecular charge transfer (ICT) from the ONa groups to the inner benzene rings.

Share and Cite:

I. Yamaguchi and K. Tsuchie, "Synthesis and Solvatochromic Behavior of Hexaphenylbenzenes and Indeno[1,2-b]fluorene Derivatives with Hydroxy Groups," International Journal of Organic Chemistry, Vol. 2 No. 3, 2012, pp. 178-187. doi: 10.4236/ijoc.2012.23027.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] M. Era, T. Tsutsui and S. Saito, “Polarized Electroluminescence from Oriented p-Wexiphenyl Vacuum—deposited Film,” Applied Physics Letters, Vol. 67, No. 17, 1995, pp. 2436-2438. doi:10.1063/1.114599
[2] J. M. Kauffman, P. T. Litak, J. A. Novinski, C. J. Kelly, A. Ghiorghis and Y. Qin, “Electronic Absorption and Emission Spectral Data and Fluorescence Quantum Yields of Bridged p-Oligophenylenes, Bi to Deciphenyls, and Related Furans and Carbazoles,” Journal Of Fluorescence, Vol. 5, No. 3, 1995, pp. 295-305. doi:10.1007/BF00723901
[3] J. M. Tour, “Conjugated Macromolecules of Precise Length and Cssonstitution. Organic Synthesis for the Construction of Nanoarchitectures,” Chemical Reviews, Vol. 96, No. 1, 1996, pp. 537-554. doi:10.1021/cr9500287
[4] F. Meghdadi, G. Leising, W. Fisher and F. Stelzer, “Multicolour Electroluminescence Diodes Using Oligophenylene and Oligophenylenevinylene Multilayers,” Synthetic Metals, Vol. 76, No. 1-3, 1996, p. 113. doi:10.1016/0379-6779(95)03430-R
[5] D. J. Grundlach, Y. Y. Lin, T. N. Jackson and D. G. Schlom, “Oligophenyl-Based Organic Thin Film Transistors,” Applied Physics Letters, Vol. 71, No. 26, 1997, pp. 3853-3855. doi:10.1063/1.120524
[6] Y. Z. Wang, R. G. Sun, F. Meghdadi, G. Leising and A. J. Epstein, “Multicolor Multilayer Light-Emitting Devices Based on Pyridine-containing Conjugated Polymers and Para-Sexiphenyl Oligomer,” Applied Physics Letters, Vol. 74, No. 24, 1999, pp. 3613-3615. doi:10.1063/1.123198
[7] R. E. Martin and F. Diederich, “Linear Monodisperse π-Conjugated Oligomers: Model Compounds for Polymers and More,” Angewandte Chemie International Edition, Vol. 38, No. 10, 1999, pp. 1350-1377. doi:10.1002/(SICI)1521-3773(19990517)38:10
[8] V. Sidorov, T. Douglas, S. M. Dzekunov, D. Abdallah, B. Ghebremariam, P. D. Roepe and S. Matile, “Self-Assembled Single-Chain Oligo(p-Phenylene) Amphiphiles: Reversed Micelles, Vesicles and Gels,” Chemical Communications, No. 15, 1999, pp. 1429-1430. doi:10.1039/A903041G
[9] B. Baumeister and S. Matile, “Programmed Assembly of Expanded Rigid-Rod β-Barrels by Supramolecular Preorganization,” Chemical Communications, No. 11, 2000, pp. 913-914. doi:10.1039/B002113J
[10] B. Baumeister, N. Sakai, S. Matile, “Giant Artificial Ion Channels Formed by Self-Assembled, Cationic Rigid- Rod β-Barrels,” Angewandte Chemie International Edition, Vo. 39, No. 11, 2000, pp. 1955-1958. doi:10.1002/1521-3773(20000602)39:11
[11] R. L. Carroll and C. B. Gorman, “The Genesis of Molecular Electronics,” Angewandte Chemie International Edition, Vol. 41, No. 23, 2002, 4378-4400. doi: 10.1002/1521-3773(20021202)41:23
[12] O. Deeg, P. Kirsch, D. Pauluth and P. B?uerle, “Combi- natorial Parallel Synthesis and Automated Screening of a Novel Class of Liquid Crystalline Materials,” Chemical Communications, No. 23, 2002, pp. 2762-2763. doi:10.1039/B207630F
[13] Z. N. Yu, H. L. Tu, X. H. Wan, Z. F. Chen and Q. F. Zhou, “Synthesis and Properties of Liquid Crystalline 4,4''-Dialkoxy-2''-Methyl-P-Terphenyls,” Molecular Crystals and Liquid Crystals, Vol. 391, No. 1, 2002, pp. 41-55. doi:10.1080/15421400390193567
[14] Z.-H. Li, M.-S. Wong, Y. Tao and M. D’Iorio, “Synthesis and Functional Properties of Strongly Luminescent Diphenylamino End-Capped Oligophenylenes,” Journal of Organic Chemistry, Vol. 69, No. 3, 2004, pp. 921-927. doi:10.1021/jo035147y
[15] K.-H. Ahn, G. Y. Ryu, S.-W. Youn and D.-M. Shin, “The Conjugation Effects on the Luminescence Properties of Oligophenylenes for the OLED,” Materials Science and Engineering: C, Vol. 24, No. 1-2, 2004, pp. 163-165. doi: 10.1016/j.msec.2003.09.010
[16] A. P. H. J. Schenning and E. W. Meijer, “Supramolecular Electronics; Nanowires from Self-Assembled π-Conjugated Systems,” Chemical Communications, No. 26, 2005, pp. 3245-3258. doi: 10.1039/B501804H
[17] H. Yin, G.-I. Lee, K. A. Sedey, O. Kutzki, H. S. Park, B. P. Orner, J. T. Ernst, H.-G. Wang, S. M. Sebti and A. D. Hamilton, “Terphenyl-Based Bak BH3 α-Helical Proteomimetics as Low-Molecular-Weight Antagonists of Bcl- x,” Journal of American Chemical Society, Vol. 127, No. 29, 2005, pp. 10191-10196. doi:10.1021/ja050122x
[18] N. H. Sultana, S. M. Kelly, B. Mansoor and N. O’Neill, “Polycatenar Oligophenylene Liquid Crystals,” Liquid Crystals, Vol. 34, No. 11, 2007, pp. 1307-1316. doi:10.1080/02678290701682357
[19] I. Yamaguchi, K. Goto and M. Sato, “Synthesis of Oligophenylenes Containing Hy-droxyl Group and Their Solvatochromic Behavior,” Tetrahedron, Vol. 65, No. 18, 2009, pp. 3645-3654. doi:10.1016/j.tet.2009.02.073
[20] I. Yamaguchi, K. Seo and Y. Kawashima, “Synthesis of Dihydroxyoligophenylenes Containing π-Deficient or π- Excess Hetero-Aromatic Rings and Their Solvatochromic Behavior,” Tetrahedron, Vol. 34, No. 7, 2010, pp. 6725- 6732. doi:10.1016/j.tet.2010.06.087
[21] A. J. Berresheim, M. Müller and K. Müllen, “Poly-phenylene Nanostructures,” Chemical Reviews, Vol. 99, No. 7, 1999, pp. 17471786. doi:10.1021/cr970073+
[22] V. Garg, “Design and Synthesis of Hexaphenylbenzene Based Artificial Photosynthetic Antenna-Reaction Centers,” Umi Dissertation Publishing, Proquest, 2011.
[23] K. E. Maly, E. Gagnon, T. Maris and J. D. Wuest, “Engineering Hydrogen-Bonded Molecular Crystals Built from Derivatives of Hexaphenylbenzene and Related Compounds,” Journal of American Chemical Society, Vol. 129, No. 14, 2007, pp. 4306-4322. doi:10.1021/ja067571x
[24] K. Kobayashi, T. Shirasaka, A. Sato, E. Horn and N. Furukawa, “Self-Assembly of a Radially Functionalized Hexagonal Molecule: Hexakis(4-hydroxyl-phenyl)ben-zene,” Angewandte Chemie International Edition, Vol. 38, No. 23, 1999, pp. 3483-3486. doi:10.1002/(SICI)1521-3773(19991203)38:23
[25] Y. Xia, Z. He, J. Tong, B. Li, C. Wang, Y. Cao, H. Wu, H. Y. Woo and D. Fan, “Synthesis and Photovoltaic Properties of Alternating Conjugated Polymers Derived from Indeno[1,2-b]fluorene and Bithiophene or Thieno[3,2- b]thiophene-Cored Benzothiadiazole,” Macromolecular Chemistry and Physics, Vol. 212, No. 11, 2011, pp. 1193- 1201. doi:10.1002/macp.201000759
[26] E. Jeong, S. H. Kim, I. H. Jung, Y. Xia, K. Lee, H. Suh, H.-K. Shim and H. Y. Woo, “Synthesis and Characterization of Indeno[1,2-b]fluorene-based White Light-Emitting Copolymer,” Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, No. 14, 2009, pp. 3467-3479. doi:10.1002/pola.23422
[27] S. H. Wadumethrige and R. Rathore, “A Facile Synthesis of Elusive Alkoxy-Substituted Hexa-peri-hexabenzocoronene,” Organic Letters, Vol. 10, No. 22, 2008, pp. 5139-5142. doi: 10.1021/ol8020429
[28] N. I. Nijegorodov, W. S. Downey and M. B. Danailov, “Systematic Investigation of Absorption, Fluorescence and Laser Properties of Some p- and m-Oligophenylenes,” Spectrochimica Acta A, Vol. 56, No. 4, 2000, pp. 783-795. doi:10.1016/S1386-1425(99)00167-5
[29] X. Zhang, A. S. Shetty and S. A. Jenekhe, “Electroluminescence and Photophysical Properties of Polyquinolines,” Macromolecules, Vol. 32, No. 22, 1999, pp. 7422- 7429. doi:10.1021/ma990960+

Copyright © 2024 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.