并五苯

并五苯
识别
CAS号	135-48-8
PubChem	8671
ChemSpider	8347
SMILES	c1ccc2cc3cc4cc5ccccc5cc4cc3cc2c1;
InChI	1/C22H14/c1-2-6-16-10-20-14-22-12-18-8-4-3-7-17(18)11-21(22)13-19(20)9-15(16)5-1/h1-14H;
InChIKey	SLIUAWYAILUBJU-UHFFFAOYAR
ChEBI	33148
性质
化学式	C22H14
摩尔质量	278.36 g/mol g·mol⁻¹
外观	暗紫色粉末
密度	1.3 g/cm3
熔点	> 300 °C; 于372 °C升华
结构
晶体结构	三斜晶系
空间群	P-1
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

并五苯（英语：Pentacene）是一种五个苯环由直线状稠合组成的一种多环芳香烃，化学式C₂₂H₁₄。并五苯对光和氧气敏感，市售并五苯常因氧化而表面带绿色。并五苯是一种有机半导体。

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合成

最初的使用合成路线在1961年提出，由邻苯二甲醛与1,4-环己二酮通过羟醛缩合得并五苯醌，再由铝汞齐还原得并五苯。^[1]

另一种合成法首先得到一个羰基桥环的前体化合物，再于150℃^[2]，或经光照^[3]失1分子CO，得并五苯。该前体化合物溶于氯仿，而并五苯不溶于一般有机溶剂，因此该法适用于以旋转涂覆制得并五苯薄膜。并五苯溶于热的氯代苯，可用1,2,4-三氯苯作溶剂重结晶。

衍生物

6,13-取代并五苯通过芳基或炔基亲核试剂（如格氏试剂与有机锂试剂）与并五苯醌的反应,随后经芳构化的还原反应得到。^[4]^[5]^[6]由二炔与环戊二烯基锆反应生成金属有机化合物中间体，再与丁炔二酸二甲酯反应，得到的酯又可通过碳链增长生成二炔，经此同系化步骤可得多取代并五苯。^[7]^[8]^[9]^[10]^[11]通过引入不同官能团，达到控制化合物颜色，电化学性质和晶体中分子排列的目的。^[12]^[13]通过取代基的选择（包括大小和位置）能控制衍生物采用一维抑或二维共面的堆积，这与并五苯晶体中人字形排列的分子相异。

虽然并五苯的结构类似于其他芳香族化合物如蒽，但其对其芳香性的解释还不完善。因此，并五苯及其衍生物是许多研究的主题。

6-亚甲基-6,13-二氢并五苯与6-甲基并五苯间存在以下平衡：

常温下此平衡极大偏向于亚甲基方向。在溶液中加热至°C时，有少量亚甲基异构体转化为甲基异构体，此时溶液显红紫色。根据一项研究，^[14]此反应的机理不是分子内H[1,5]σ迁移，而是双分子自由基的氢迁移。相比之下，结构类似异甲苯（亚甲基环己二烯）则相当不稳定。

并五苯与硫在1,2,4 - 三氯苯中反应得六硫并五苯.^[15] X射线晶体衍射实验结果显示所有的碳硫键键长相似（170 pm），从共振论的角度解释，电荷分离的两种共振式B、C的贡献比结构A更大。

晶相中相邻分子的硫原子间距（337 pm）小于分子的范德华半径（180 pm）的两倍，这是由于相邻分子间存在π重叠的缘故。作为有机半导体，此性质与四硫富瓦烯相似。

并五苯骨架平面看上去是刚性的，但事实上，大取代基可以使其变得相当扭曲：^[16]

由于六个苯基的存在，骨架两端扭曲达144°，此化合物具有光学活性，可拆分为一对旋光异构体，旋光度高达7400°，其外消旋化半衰期为9小时。

应用

并五苯是一种潜在的二色性染料。^[17]^[18]

并五苯与富勒烯结合，用于有机光伏电池的研究。^[17]^[18]

并五苯是有机薄膜晶体管(OTFT)和有机场效应晶体管(OFET)研究的主流半导体材料，是研究最全面深入的共轭有机分子(conjugated organic molecules）。由于其作为有机场效应晶体管的空穴迁移率最高可达5.5 cm²/(V·s)，超过了非晶硅，具有很大的应用前景。^[19]^[20]^[21]

并五苯以及其他有机半导体在空气中会迅速氧化，故其作为有机半导体的商业价值不高。但其经氧化处理得到的并五苯醌具有栅极绝缘膜方面的应用价值^[20]

参见

全氟并五苯

参考资料

[1]
Bruckner, V.; Tomasz, J. Acta. Chim. Hung. 1961, 28, 405–408.
[2]
Chen, Kew-Yu; Hsieh, HH; Wu, CC; Hwang, JJ; Chow, TJ. A new type of soluble pentacene precursor for organic thin-film transistors. Chemical Communications. 2007, (10): 1065–7. PMID 17325807. doi:10.1039/b616511g.
[3]
Yamada, H.; Yamashita, Y.; Kikuchi, M.; Watanabe, H.; Okujima, T.; Uno, H.; Ogawa, T.; Ohara, K.; Ono, N. "Photochemical Synthesis of Pentacene and its Derivatives." Chem. Eur. J. 2005, 11, 6212–6220. doi:10.1002/chem.200500564
[4]
Allen, C. F. H.; Bell, Alan. Journal of the American Chemical Society. 1942, 64 (6): 1253. doi:10.1021/ja01258a005. 缺少或|title=为空 (帮助)
[5]
Maulding, D. R.; Roberts, Bernard G. Electronic absorption and fluorescence of phenylethynyl-substituted acenes. The Journal of Organic Chemistry. 1969, 34 (6): 1734. doi:10.1021/jo01258a045.
[6]
Li, Shi; Zhou, Lishan; Nakajima, Kiyohiko; Kanno, Ken-Ichiro; Takahashi, Tamotsu. Synthesis of 1,2,3,4,8,9,10,11-Octasubstituted Pentacenequinone Derivatives and their Conversion into Substituted Pentacenes. Chemistry – an Asian Journal. 2010, 5 (7): 1620–6. PMID 20455241. doi:10.1002/asia.200900754.
[7]
Takahashi, Tamotsu; Kitamura, Masanori; Shen, Baojian; Nakajima, Kiyohiko. Straightforward Method for Synthesis of Highly Alkyl-Substituted Naphthacene and Pentacene Derivatives by Homologation. Journal of the American Chemical Society. 2000, 122 (51): 12876. doi:10.1021/ja003130g.
[8]
Takahashi, Tamotsu; Li, Shi; Huang, Wenying; Kong, Fanzhi; Nakajima, Kiyohiko; Shen, Baojian; Ohe, Takahiro; Kanno, Ken-Ichiro. Homologation Method for Preparation of Substituted Pentacenes and Naphthacenes. The Journal of Organic Chemistry. 2006, 71 (21): 7967–77. PMID 17025283. doi:10.1021/jo060923y.
[9]
Takahashi, Tamotsu; Li, Yanzhong; Hu, Jinghan; Kong, Fanzhi; Nakajima, Kiyohiko; Zhou, Lishan; Kanno, Ken-Ichiro. Cu(I)-mediated cycloaddition reaction of zirconacyclopentadienes with fumaronitrile and application for synthesis of monocyano-substituted pentacenes. Tetrahedron Letters. 2007, 48 (38): 6726. doi:10.1016/j.tetlet.2007.07.075.
[10]
Stone, Matthew T.; Anderson, Harry L. Three-Step Synthesis of End-Substituted Pentacenes. The Journal of Organic Chemistry. 2007, 72 (25): 9776–8. PMID 17999529. doi:10.1021/jo7017284.
[11]
Li, Shi; Li, Zhiping; Nakajima, Kiyohiko; Kanno, Ken-Ichiro; Takahashi, Tamotsu. Double Homologation Method for Substituted Soluble Pentacenes and Dimerization Behaviours of Pentacenes. Chemistry – an Asian Journal. 2009, 4 (2): 294–301. PMID 19072938. doi:10.1002/asia.200800312.
[12]
Anthony, J. E.; Brooks, J. S.; Eaton, D. L.; Parkin, S. R. Functionalized Pentacene: Improved Electronic Properties from Control of Solid-State Order. Journal of the American Chemical Society. 2001, 123 (38): 9482–9483 [2013-07-27]. PMID 11562247. doi:10.1021/ja0162459. （原始内容存档于2017-05-21）.
[13]
Anthony, J. E.; Eaton, D. L.; Parkin, S. R. A Road Map to Stable, Soluble, Easily Crystallized Pentacene Derivatives. Organic Letters. 2002, 4 (1): 15–18. PMID 11772079. doi:10.1021/ol0167356.
[14]
Norton, Joseph E.; Northrop, BH; Nuckolls, C; Houk, KN. Why 6-Methylpentacene Deconjugates but Avoids the Thermally Allowed Unimolecular Mechanism. Organic Letters. 2006, 8 (21): 4915–8. PMID 17020335. doi:10.1021/ol062012g.
[15]
Briseno, Alejandro L.; Miao, Q; Ling, MM; Reese, C; Meng, H; Bao, Z; Wudl, F. Hexathiapentacene: Structure, Molecular Packing, and Thin-Film Transistors. Journal of the American Chemical Society. 2006, 128 (49): 15576–7. PMID 17147352. doi:10.1021/ja066088j..
[16]
Lu, Jun; Ho, DM; Vogelaar, NJ; Kraml, CM; Bernhard, S; Byrne, N; Kim, LR; Pascal Jr, RA. Synthesis, Structure, and Resolution of Exceptionally Twisted Pentacenes. Journal of the American Chemical Society. 2006, 128 (51): 17043–50. PMID 17177456. doi:10.1021/ja065935f.
[17]
Dissanayake, D. M. Nanditha M. Nanoimprinted large area heterojunction pentacene-C[sub 60] photovoltaic device. Applied Physics Letters. 2007, 90 (25): 253502. Bibcode:2007ApPhL..90y3502D. doi:10.1063/1.2749863.
[18]
Efficiently Organic: Researchers Use Pentacene To Develop Next-generation Solar Power sciencedaily.com Link （页面存档备份，存于互联网档案馆）
[19]
Norbert Koch. Organic Electronic Devices and Their Functional Interfaces. ChemPhysChem. 2007, 8 (10): 1438–55. PMID 17539032. doi:10.1002/cphc.200700177.
[20]
Tatsuo Hasegawa and Jun Takeya. Organic field-effect transistors using single crystals. Sci. Technol. Adv. Mater. 2009, 10 (2): 024314. Bibcode:2009STAdM..10b4314H. doi:10.1088/1468-6996/10/2/024314.
[21]
Yoshiro Yamashita. Organic semiconductors for organic field-effect transistors. Sci. Technol. Adv. Mater. 2009, 10 (2): 024313. Bibcode:2009STAdM..10b4313Y. doi:10.1088/1468-6996/10/2/024313.

外部链接

facts about pentacene （页面存档备份，存于互联网档案馆）, retrieved Apr. 17, 2006
Organic transistor improves with age （页面存档备份，存于互联网档案馆）, New Scientist, 2 December 2007
Pentacene Imaged （页面存档备份，存于互联网档案馆）, IBM images Pentacene, the first molecule imaged in detail 29 August 2009

[1] [1]
Bruckner, V.; Tomasz, J. Acta. Chim. Hung. 1961, 28, 405–408.

[Chen-2] [2]
Chen, Kew-Yu; Hsieh, HH; Wu, CC; Hwang, JJ; Chow, TJ. A new type of soluble pentacene precursor for organic thin-film transistors. Chemical Communications. 2007, (10): 1065–7. PMID 17325807. doi:10.1039/b616511g.

[3] [3]
Yamada, H.; Yamashita, Y.; Kikuchi, M.; Watanabe, H.; Okujima, T.; Uno, H.; Ogawa, T.; Ohara, K.; Ono, N. "Photochemical Synthesis of Pentacene and its Derivatives." Chem. Eur. J. 2005, 11, 6212–6220. doi:10.1002/chem.200500564

[4] [4]
Allen, C. F. H.; Bell, Alan. Journal of the American Chemical Society. 1942, 64 (6): 1253. doi:10.1021/ja01258a005. 缺少或|title=为空 (帮助)

[5] [5]
Maulding, D. R.; Roberts, Bernard G. Electronic absorption and fluorescence of phenylethynyl-substituted acenes. The Journal of Organic Chemistry. 1969, 34 (6): 1734. doi:10.1021/jo01258a045.

[6] [6]
Li, Shi; Zhou, Lishan; Nakajima, Kiyohiko; Kanno, Ken-Ichiro; Takahashi, Tamotsu. Synthesis of 1,2,3,4,8,9,10,11-Octasubstituted Pentacenequinone Derivatives and their Conversion into Substituted Pentacenes. Chemistry – an Asian Journal. 2010, 5 (7): 1620–6. PMID 20455241. doi:10.1002/asia.200900754.

[7] [7]
Takahashi, Tamotsu; Kitamura, Masanori; Shen, Baojian; Nakajima, Kiyohiko. Straightforward Method for Synthesis of Highly Alkyl-Substituted Naphthacene and Pentacene Derivatives by Homologation. Journal of the American Chemical Society. 2000, 122 (51): 12876. doi:10.1021/ja003130g.

[8] [8]
Takahashi, Tamotsu; Li, Shi; Huang, Wenying; Kong, Fanzhi; Nakajima, Kiyohiko; Shen, Baojian; Ohe, Takahiro; Kanno, Ken-Ichiro. Homologation Method for Preparation of Substituted Pentacenes and Naphthacenes. The Journal of Organic Chemistry. 2006, 71 (21): 7967–77. PMID 17025283. doi:10.1021/jo060923y.

[9] [9]
Takahashi, Tamotsu; Li, Yanzhong; Hu, Jinghan; Kong, Fanzhi; Nakajima, Kiyohiko; Zhou, Lishan; Kanno, Ken-Ichiro. Cu(I)-mediated cycloaddition reaction of zirconacyclopentadienes with fumaronitrile and application for synthesis of monocyano-substituted pentacenes. Tetrahedron Letters. 2007, 48 (38): 6726. doi:10.1016/j.tetlet.2007.07.075.

[10] [10]
Stone, Matthew T.; Anderson, Harry L. Three-Step Synthesis of End-Substituted Pentacenes. The Journal of Organic Chemistry. 2007, 72 (25): 9776–8. PMID 17999529. doi:10.1021/jo7017284.

[11] [11]
Li, Shi; Li, Zhiping; Nakajima, Kiyohiko; Kanno, Ken-Ichiro; Takahashi, Tamotsu. Double Homologation Method for Substituted Soluble Pentacenes and Dimerization Behaviours of Pentacenes. Chemistry – an Asian Journal. 2009, 4 (2): 294–301. PMID 19072938. doi:10.1002/asia.200800312.

[12] [12]
Anthony, J. E.; Brooks, J. S.; Eaton, D. L.; Parkin, S. R. Functionalized Pentacene: Improved Electronic Properties from Control of Solid-State Order. Journal of the American Chemical Society. 2001, 123 (38): 9482–9483 [2013-07-27]. PMID 11562247. doi:10.1021/ja0162459. （原始内容存档于2017-05-21）.

[13] [13]
Anthony, J. E.; Eaton, D. L.; Parkin, S. R. A Road Map to Stable, Soluble, Easily Crystallized Pentacene Derivatives. Organic Letters. 2002, 4 (1): 15–18. PMID 11772079. doi:10.1021/ol0167356.

[14] [14]
Norton, Joseph E.; Northrop, BH; Nuckolls, C; Houk, KN. Why 6-Methylpentacene Deconjugates but Avoids the Thermally Allowed Unimolecular Mechanism. Organic Letters. 2006, 8 (21): 4915–8. PMID 17020335. doi:10.1021/ol062012g.

[15] [15]
Briseno, Alejandro L.; Miao, Q; Ling, MM; Reese, C; Meng, H; Bao, Z; Wudl, F. Hexathiapentacene: Structure, Molecular Packing, and Thin-Film Transistors. Journal of the American Chemical Society. 2006, 128 (49): 15576–7. PMID 17147352. doi:10.1021/ja066088j..

[16] [16]
Lu, Jun; Ho, DM; Vogelaar, NJ; Kraml, CM; Bernhard, S; Byrne, N; Kim, LR; Pascal Jr, RA. Synthesis, Structure, and Resolution of Exceptionally Twisted Pentacenes. Journal of the American Chemical Society. 2006, 128 (51): 17043–50. PMID 17177456. doi:10.1021/ja065935f.

[#1-17] [17]
Dissanayake, D. M. Nanditha M. Nanoimprinted large area heterojunction pentacene-C[sub 60] photovoltaic device. Applied Physics Letters. 2007, 90 (25): 253502. Bibcode:2007ApPhL..90y3502D. doi:10.1063/1.2749863.

[#2-18] [18]
Efficiently Organic: Researchers Use Pentacene To Develop Next-generation Solar Power sciencedaily.com Link （页面存档备份，存于互联网档案馆）

[19] [19]
Norbert Koch. Organic Electronic Devices and Their Functional Interfaces. ChemPhysChem. 2007, 8 (10): 1438–55. PMID 17539032. doi:10.1002/cphc.200700177.

[sc-20] [20]
Tatsuo Hasegawa and Jun Takeya. Organic field-effect transistors using single crystals. Sci. Technol. Adv. Mater. 2009, 10 (2): 024314. Bibcode:2009STAdM..10b4314H. doi:10.1088/1468-6996/10/2/024314.

[pc-21] [21]
Yoshiro Yamashita. Organic semiconductors for organic field-effect transistors. Sci. Technol. Adv. Mater. 2009, 10 (2): 024313. Bibcode:2009STAdM..10b4313Y. doi:10.1088/1468-6996/10/2/024313.

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