In the presence of RhCl3 center dot 3H(2)O and i-Pr2NEt, the cyclotrimerization of di(2-thienyl)acetylenes proceeded smoothly to afford hexa(2-thienyl)benzenes. CV analysis of the hexa(2-thienyl)benzenes showed that they may be useful as electroactive materials.</p

Abruña

Assaka

Baumgatner

Carpi

Chebny

Chen

Coppo

Dini

Geng

Guerrero

Hideo Tanaka

Ichiro Morimoto

Kenta Yoshida

Koichi Mitsudo

Loveday

Mamane

Neef

Rosokha

Suematsu

Wohlgenanut

Yoshida

English

Yoshida, Kenta

Morimoto, Ichiro

Mitsudo, Koichi

Tanaka, Hideo

Okayama University Digital Information Repository

Facile synthetic procedure for and electrochemical properties of hexa(2-thienyl)benzenes directed toward electroactive materials

Okayama University Scientific Achievement Repository

ChemistryOrganic Chemistry fieldsOkayama University Year 2008Facile synthetic procedure for andelectrochemical properties ofhexa(2-thienyl)benzenes directed towardelectroactive materialsKenta Yoshida∗ Ichiro Morimoto†Koichi Mitsudo‡ Hideo Tanaka∗∗∗Division of Chemistry and Biochemistry, Graduate School of Natural Science and Tech-nology, Okayama University†Division of Chemistry and Biochemistry, Graduate School of Natural Science and Tech-nology, Okayama University‡Division of Chemistry and Biochemistry, Graduate School of Natural Science and Tech-nology, Okayama University, mitsudo@cc.okayama-u.ac.jp∗∗Division of Chemistry and Biochemistry, Graduate School of Natural Science and Tech-nology, Okayama University, tanaka95@cc.okayama-u.ac.jpThis paper is posted at eScholarship@OUDIR : Okayama University Digital InformationRepository.http://escholarship.lib.okayama-u.ac.jp/organic chemistry/9Graphical Abstract Facile synthetic procedure for and electrochemical properties of hexa(2-thienyl)benzenes directed towards electroactive materials Kenta Yoshida, Ichiro Morimoto, Koichi Mitsudo,*   Hideo Tanaka*  Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan   Leave this area blank for abstract info. RhCl3·3H2O  (8 mol %)i-Pr2NEt (30 mol %)πππππππ =S Rππ   1 Facile synthetic procedure for and electrochemical properties of hexa(2-thienyl)benzenes directed towards electroactive materials Kenta Yoshida, Ichiro Morimoto, Koichi Mitsudo,* Hideo Tanaka* Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan  Abstract— In the presence of RhCl3•3H2O and i-Pr2NEt, the cyclotrimerization of di(2-thienyl)acetylenes proceeded smoothly to afford hexa(2-thienyl)benzenes. CV analysis of the hexa(2-thienyl)benzenes showed that they may be useful as electroactive materials. © 2008 Elsevier Science. All rights reserved Keywords: Rh/amine catalyst; Cyclotrimerization; Hexa(2-thienyl)benzene; Electroactive material.  ——— Corresponding authors. Tel.: +81-86-251-8072; fax: +81-86-251-8079. E-mail addresses: tanaka95@cc.okayama-u.ac.jp (H. Tanaka), mitsudo@cc.okayama-u.ac.jp (K. Mitsudo) Over the past decade, extended π-conjugated compounds1 have been studied for use as materials in organic electroluminescent devices2,3 and energy storage devices.4,5 Recently, two-dimensional aromatic cores, such as starburst hexaarylbenzene derivatives, have been synthesized, and their electrochemical and photochemical properties have been intensively studied.6 However, there have been only a few reports on the construction of hexaheteroarylbenzenes, such as hexa(2-thienyl)benzene derivatives, because they are difficult to synthesize. One way to construct hexathienylbenzene derivatives is Stille-type coupling of hexabromobenzene and thienylstannane, wherein the reaction should use a large amount of toxic stannanes.7 Another way is transition metals-catalyzed cyclotrimerization of dithienylacetylenes.8 However, the trimerization of internal alkynes bearing heteroaryl groups is inhibited by the steric hindrance of products and the coordination of hetero-atoms to the central metal of the catalyst. For instance, Weber and co-workers reported that the reaction of di-2-thienylacetylene catalyzed by RuH2(CO)(PPh3)3 gave a dimerized product, a benzothiophene derivative, as the major product (63%) and hexa(2-thienyl)benzene was obtained in only 5% yield.8a One approach to solving this problem is to introduce large substituents at the 5-position of thiophene moieties. Müllen and co-workers reported that Co2(CO)8 catalyzed the cyclization of di(5-n-C12H25-thiophen-2-yl)acetylene to give hexathienylbenzene derivatives in 61% yield.8b To our knowledge, there are no other reports on the efficient construction of hexathienylbenzene derivatives, although they should be novel, intriguing building blocks for not only electroactive materials but also photo-materials. Recently, we found that the cyclotrimerization of internal alkynes proceeds efficiently in the presence of the RhCl3/i-Pr2NEt catalyst.9 These successful results prompted us to investigate the application of our methods to the synthesis of hexathienylbenzene derivatives. We report here the RhCl3/i-Pr2NEt-catalyzed cyclotrimerization of di(2-thienyl)acetylenes, and the electrochemical properties of the resulting starburst-type benzene derivatives. First, we performed the trimerization of di(2-thienyl)acetylene 1a (Scheme 1). In the presence of RhCl3•3H2O (8 mol %) and i-Pr2NEt (30 mol %), a solution of di(2-thienyl)acetylene (1a) in toluene was heated to reflux for 24 h to afford hexa(2-thienyl)benzene (2a)10 in 14% yield and 44% of 1a was recovered. Although the dimerization did not take place, as we expected, the yield of 2a was unsatisfactory. The low reactivity might be attributable to the coordination of a thienyl group to the Rh center. To suppress this coordination, we next used i-PrOH as a solvent, and the yield of 2a increased to 49%.    2 RhCl3·3H2O  (8 mol %)i-Pr2NEt (30 mol %)reflux, 24 h14% (solvent = toluene)49% (solvent = i-PrOH)1aS SSSSSSS2a Scheme 1. RhCl3/i-Pr2NEt-catalyzed cyclotrimerization of 1a. To evaluate the catalytic activity of RhCl3/i-Pr2NEt, the cyclotrimerization of 1a was carried out using several catalysts (Table 1). Notably, the reaction using RhCl3•3H2O in i-PrOH showed higher reactivity than with other catalysts which are frequently used for the trimerization reaction of acetylene derivatives (entry 1). With toluene or 1,4-dioxane as a solvent, the yield of 2a decreased (entries 2 and 3). When the reaction was carried out using RhCl(PPh3)3 (Wilkinson’s catalyst) in i-PrOH or toluene, 2a was obtained in respective yields of only 5% and 26% (entries 4 and 5). [Rh(cod)2][BF4] (cationic catalyst) was ineffective, and starting material 1a was recovered (entries 6 and 7). When Co2(CO)8 was used in i-PrOH, the corresponding product was not obtained at all (entry 8). With 1,4-dioxane as a solvent, the corresponding product was obtained in 37% yield (entry 9). It is likely that RhCl3/i-Pr2NEt catalyst might be electron-rich due to the coordination of i-Pr2NEt, and could promote the efficient formation of metallacycle intermediates. Table 1 Cyclotrimerization of 1a using several catalysts  catalyst (8 mol %)solvent, refluxAr ArArArArArArArSAr1a2a  Entry Catalyst Solvent Time (h) Yield  (%)a Recov. 1a (%)a  1 RhCl3·3H2O/i-Pr2NEt i-PrOH 24 49 49 2 RhCl3·3H2O/i-Pr2NEt Toluene 24 14 44 3 RhCl3·3H2O/i-Pr2NEt Dioxane 24 11 87 4 RhCl(PPh3)3 i-PrOH 24 5 73 5 RhCl(PPh3)3 Toluene 48 26 54 6 [Rh(cod)2][BF4] i-PrOH 24 - 68 7 [Rh(cod)2][BF4] Toluene 48 - 71 8 Co2(CO)8 i-PrOH 24 - - 9 Co2(CO)8 Dioxane 24 37 - a Isolated yield.  In a similar manner, we performed the cyclotrimerization of di(2-thienyl)acetylenes bearing substituents on the 5-position of their thienyl groups (Table 2). In toluene and i-PrOH, the cyclotrimerization of alkyne 1b, bearing a 5-methylthienyl group, gave the cycloadduct in respective yields of 63% and 50% (entries 1 and 2).11 Notably, the reactivity of 1b in toluene was similar to that in i-PrOH, which is different from that of 1a, probably because the methyl group on α-position of thienyl group might reduce the coordination ability of the thienyl group. Indeed, in toluene, the cyclotrimerization of alkyne 1c, bearing a 5-acetylthienyl group which also can coordinate to the Rh center, gave cycloadduct 2c12 in only 4% yield and 1c was recovered in 20% yield (entry 3). With i-PrOH as a solvent, the yield of 2c dramatically increased to 50% (entry 4). These results suggest that RhCl3/i-Pr2NEt catalyst might be more active in toluene than i-PrOH, but i-PrOH would suppress the coordination of a thienyl group to the Rh center.     3Table 2 RhCl3/i-Pr2NEt-catalyzed cyclotrimerization of 1 Ar ArRhCl3·3H2O  (8 mol %)i-Pr2NEt (30 mol %)ArArArArArArS RAr12solvent, reflux, 24 h  Entry 1 R Solvent 2 Yield (%)a Recov. 1 (%)a 1 1b Me Toluene 2b 63 - 2 1b Me i-PrOH 2b 50 18 3 1c Ac Toluene 2c 4 20 4 1c Ac i-PrOH 2c 50 - a Isolated yield.  Next, we subjected 2a to cyclic voltammetry (CV) measurements (Fig. 1). The growth of redox waves was observed in the potential range from 0.2 to 0.8 V during the sequential potential cycling (×100), which suggested the formation of an electroactive film on the surface of the working electrode. In fact, a film was observed on the surface of the electrode. This suggests that the extension of π-conjugation of 2a might occur during the electrooxidation. Next, to investigate the main coupling position of a 2a-based film, we measured the CV of 2b bearing a methyl group at the 5-position of the thienyl groups. In CV, no significant increase in redox waves was observed, which suggests that electrooligomerization might occur at the 5-position of the thienyl groups. No film was observed on the working electrode during the electrooxidation of 2b.  Fig. 1. Cyclic voltammograms of 2a (10 mM) in TEABF4/PC (1 M) solution.  Scan rate: 100 mVs-1.  The generated film was then subjected to CV analysis (Fig. 2). CV of the film showed two distinct redox responses: one in the potential range from 0.2 to 0.8 V (p-doping), and the other from −1.5 V to −2.8 V (n-doping), which are similar to those of frequently used polythiophene derivatives reported by Ferraris.13 The maximum potential difference between redox waves of n- and p-doping were 3.5 V, which indicated a 3.5-eV band gap. -4.0-2.00.02.04.0-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0Potential / V vs. Ag/Ag+Current density/ mA cm-2  Fig. 2. CVs of 2a-based film formed after CVs in Fig. 1. Electrolyte: 2a (10 mM) in TEABF4/PC (1 M) solution. Scan rate: 100 mVs-1. Number of cycling: 5th cycle.  In summary, a simple method for constructing hexathienylbenzenes has been developed, and their fundamental electrochemical properties have been clarified. We found that hexa(2-thienyl)benzene (2a) generated films by sequential potential cycling (CV). Though the exact structure of the film has not been clear yet, it should be a novel type polymer or oligomer containing thiophene linked at 2 and 5 positions. In addition, these 2a-based films may be a candidate for the electroactive materials in energy storage devices. Further studies on hexaheteroarylbenzenes are underway in our laboratory.   Acknowledgments We thank the SC-NMR Laboratory of Okayama University for 1H and 13C NMR analyses.  References 1. For a review, see: Baumgatner, T.; Réau, R. Chem. Rev. 2006, 106, 4681−4727. 2. For a review, see: Dini, D. Chem. Mater. 2005, 17, 1933−1945. -20246-0.5 0.0 0.5 1.0Potential / V vs. Ag/Ag+Current density / mA cm-23. (a) Carpi, F.; Rossi, D. D. Opt. Laser Technol. 2006, 38, 292−305; (b) Assaka, A. M.; Rodrigues, P. C.; Oliveira, A. R. M.; Ding, L.; Hu, B.; Karasz, F. E; Akcelrud, L. Polymer 2004, 45, 7071−7081. 4. For reviews, see: (a) Wohlgenanut, M.; Vardeny, Z. V. J. Phys.: Condens. Matte. 2003, 15, R83−R107; (b) Abruña, H. D.; Matsumoto F.; Cohen, J. L.; Jin, J.; Roychowdhury, C.; Prochaska, M.; van Dover, R. B.; DiSalvo, F. J.; Kiya, Y.; Henderson, J. C.; Hutchison, G. R. Bull. Chem. Soc. Jpn. 2007, 80, 1843−1855. 1cycle10cycle20cycle50cycle100cycle5. (a) Suematsu, S.; Mitsudo, K.; Katagiri, F.; Tanaka, H. Electrochemistry 2007, 75, 54−57; (b) Chen, T.; Wang, L.; Jiang, G.; Wang, W.; Wang, X. j.; Zhou, J.; Wang, J.; Chen, C.; Wang, W.; Gao, H. J. Electroanal. Chem. 2006, 586, 122−127; (c) Coppo, P.; Turner, M. L. J. Mater. Chem. 2005, 15, 1123−1133.    4 6. (a) Chebny, V. J.; Shukla, R.; Rathore, R. J. Phys. Chem. A 2006, 110, 13003−13006; (b) Rosokha, S. V.; Neretin, I. S.; Kochi, J. K. J. Am. Chem. Soc. 2006, 128, 9394−9407; (c) Mamane, V.; Gref, A.; Lefloch, F.; Riant, O. J. Organomet. Chem. 2001, 637, 84−88. 7. Wu, I.-Y.; Lin, J. T.; Tao, Y.-T.; Balasubramaniam, E. Adv. Mater. 2000, 12, 668−669. 8. (a) Lu, P.; Cai, G.; Li, J.; Weber, W. P. J. Heterocycl. Chem. 2002, 39, 91−92; (b) Geng, Y.; Fechtenkötter, A.; Müllen, K. J. Mater. Chem. 2001, 11, 1634−1641. 9. Yoshida, K.; Morimoto, I.; Mitsudo, K.; Tanaka, H. Chem. Lett. 2007, 36, 998−999. 10. General procedure for Rh/amine-catalyzed cyclotrimerization of alkyne 1: To a solution of RhCl3·3H2O (11 mg, 0.04 mmol) in i-PrOH (3.0 mL) were added i-Pr2NEt (26 μL, 0.15 mmol) and di(2-thienyl)acetylene 1a (96 mg, 0.50 mmol). The mixture was stirred at reflux for 24 h. After being cooled to room temperature, the reaction mixture was filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/toluene 5:1) to afford hexa(2-thienyl)benzene 2a (47 mg, 49%) as yellow solids: Rf = 0.27 (hexane/toluene 5:1); 1H NMR (600 MHz, CDCl3) δ 6.59 (dd, J = 3.6, 1.2 Hz, 6H), 6.68 (dd, J = 5.4, 3.6 Hz, 6H), 7.08 (dd, J = 5.4, 1.2 Hz, 6H); 13C NMR (150 MHz, CDCl3) δ 125.8, 126.2, 129.1, 137.0, 140.7; IR (KBr) 3068, 2923, 2360, 1647, 1381, 694 cm−1; Anal. Calcd for C30H18S6: C, 63.12; H, 3.18. Found: C, 63.08; H, 3.36. 11. Hexakis(5-methyl-2-thienyl)benzene (2b): Yellow solids; Rf = 0.23 (hexane/toluene 5:1); 1H NMR (600 MHz, CDCl3) δ 6.33 (s, 12H), 2.30 (s, 18H); 13C NMR (150 MHz, CDCl3) δ 15.2, 123.9, 128.7, 137.0, 138.8, 140.2; IR (KBr) 3068, 2912, 2855, 2357, 1747, 1442, 1219, 800 cm−1; Anal. Calcd for C36H30S6: C, 66.01; H, 4.62. Found: C, 66.09; H, 4.53. 12. Hexakis(5-acetyl-2-thienyl)benzene (2c): Colorless solids; Rf = 0.07 (hexane/EtOAc 3:1), 1H NMR (600 MHz, CDCl3) δ 7.27 (d, J = 3.6 Hz, 6H), 6.67 (d, J = 3.6 Hz, 6H), 2.43 (s, 18H); 13C NMR (150 MHz, CDCl3) δ 26.7, 130.9, 131.8, 136.5, 145.8, 146.7, 190.7; IR (KBr) 3080, 1658, 1471, 1381, 1274 cm−1. 13. (a) Neef, C. J.; Brotherston, I. D.; Ferraris, J. P. Chem. Mater. 1999, 11, 1957−1958; (b) Loveday, D. C.; Hmyene, M.; Ferraris, J. P. Synth. Met. 1997, 84, 245−246; (c) Guerrero, D. J.; Ren, X.; Ferraris, J. P. Chem. Mater. 1994, 6, 1437−1443.  Supplementary Material   

15, R83−R107; (b)

3.6 Hz, 6H), 7.08 (dd,

Hexakis(5-acetyl-2-thienyl)benzene (2c): Colorless solids;

Hexakis(5-methyl-2-thienyl)benzene (2b): Yellow solids; Rf =

Potential / V vs. Ag/Ag + C u r r e n t d e n s i t y / m A c m -2

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Facile synthetic procedure for and electrochemical properties of hexa(2-thienyl)benzenes directed toward electroactive materials

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