駢五苯

駢五苯
識別
CAS編號	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
性質
化學式	C22H14
莫耳質量	278.36 g/mol g·mol⁻¹
外觀	暗紫色粉末
密度	1.3 g/cm3
熔點	> 300 °C; 於372 °C升華
結構
晶體結構	三斜晶系
空間群	P-1
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

駢五苯（英語：Pentacene）是一種五個苯環由直線狀稠合組成的一種多環芳香烴，化學式C₂₂H₁₄。駢五苯對光和氧氣敏感，市售駢五苯常因氧化而表面帶綠色。駢五苯是一種有機半導體。

合成[編輯]

最初的使用合成路線在1961年提出，由鄰苯二甲醛與1,4-環己二酮通過羥醛縮合得駢五苯醌，再由鋁汞齊還原得駢五苯。^[1]

另一種合成法首先得到一個羰基橋環的前體化合物，再於150℃^[2]，或經光照^[3]失1分子CO，得駢五苯。該前體化合物溶於氯仿，而駢五苯不溶於一般有機溶劑，因此該法適用於以旋轉塗覆製得駢五苯薄膜。駢五苯溶於熱的氯代苯，可用1,2,4-三氯苯作溶劑重結晶。

衍生物[編輯]

6,13-取代駢五苯通過芳基或炔基親核試劑（如格氏試劑與有機鋰試劑）與駢五苯醌的反應,隨後經芳構化的還原反應得到。^[4]^[5]^[6]由二炔與環戊二烯基鋯反應生成金屬有機化合物中間體，再與丁炔二酸二甲酯反應，得到的酯又可通過碳鏈增長生成二炔，經此同系化步驟可得多取代駢五苯。^[7]^[8]^[9]^[10]^[11]通過引入不同官能基，達到控制化合物顏色，電化學性質和晶體中分子排列的目的。^[12]^[13]通過取代基的選擇（包括大小和位置）能控制衍生物採用一維抑或二維共面的堆積，這與駢五苯晶體中人字形排列的分子相異。

雖然駢五苯的結構類似於其他芳香族化合物如蒽，但其對其芳香性的解釋還不完善。因此，駢五苯及其衍生物是許多研究的主題。

6-亞甲基-6,13-二氫駢五苯與6-甲基駢五苯間存在以下平衡：

常溫下此平衡極大偏向於亞甲基方向。在溶液中加熱至°C時，有少量亞甲基異構物轉化為甲基異構物，此時溶液顯紅紫色。根據一項研究，^[14]此反應的機理不是分子內H[1,5]σ遷移，而是雙分子自由基的氫遷移。相比之下，結構類似異甲苯（亞甲基環己二烯）則相當不穩定。

駢五苯與硫在1,2,4 - 三氯苯中反應得六硫駢五苯.^[15] X射線晶體衍射實驗結果顯示所有的碳硫鍵鍵長相似（170 pm），從共振論的角度解釋，電荷分離的兩種共振式B、C的貢獻比結構A更大。

晶相中相鄰分子的硫原子間距（337 pm）小於分子的范德華半徑（180 pm）的兩倍，這是由於相鄰分子間存在π重疊的緣故。作為有機半導體，此性質與四硫富瓦烯相似。

駢五苯骨架平面看上去是剛性的，但事實上，大取代基可以使其變得相當扭曲：^[16]

由於六個苯基的存在，骨架兩端扭曲達144°，此化合物具有光學活性，可拆分為一對旋光異構物，旋光度高達7400°，其外消旋化半衰期為9小時。

應用[編輯]

駢五苯是一種潛在的二色性染料。^[17]^[18]

駢五苯與富勒烯結合，用於有機光伏電池的研究。^[17]^[18]

駢五苯是有機薄膜電晶體(OTFT)和有機場效應電晶體(OFET)研究的主流半導體材料，是研究最全面深入的共軛有機分子(conjugated organic molecules）。由於其作為有機場效應電晶體的空穴遷移率最高可達5.5 cm²/(V·s)，超過了非晶矽，具有很大的應用前景。^[19]^[20]^[21]

駢五苯以及其他有機半導體在空氣中會迅速氧化，故其作為有機半導體的商業價值不高。但其經氧化處理得到的駢五苯醌具有柵極絕緣膜方面的應用價值^[20]

參見[編輯]

全氟駢五苯

參考資料[編輯]

^ Bruckner, V.; Tomasz, J. Acta. Chim. Hung. 1961, 28, 405–408.
^ 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.
^ 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
^ Allen, C. F. H.; Bell, Alan. Journal of the American Chemical Society. 1942, 64 (6): 1253. doi:10.1021/ja01258a005. 缺少或|title=為空 (幫助)
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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. （原始內容存檔於2017-05-21）.
^ 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.
^ 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.
^ 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. .
^ 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.
^ ^17.0 ^17.1 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.
^ ^18.0 ^18.1 Efficiently Organic: Researchers Use Pentacene To Develop Next-generation Solar Power sciencedaily.com Link （頁面存檔備份，存於網際網路檔案館）
^ Norbert Koch. Organic Electronic Devices and Their Functional Interfaces. ChemPhysChem. 2007, 8 (10): 1438–55. PMID 17539032. doi:10.1002/cphc.200700177.
^ ^20.0 ^20.1 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.
^ 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.

外部連結[編輯]

facts about pentacene （頁面存檔備份，存於網際網路檔案館）, retrieved Apr. 17, 2006
Organic transistor improves with age （頁面存檔備份，存於網際網路檔案館）, New Scientist, 2 December 2007
Pentacene Imaged （頁面存檔備份，存於網際網路檔案館）, IBM images Pentacene, the first molecule imaged in detail 29 August 2009

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

[Chen-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=為空 (幫助)

[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. （原始內容存檔於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.

[#1-17] 17.0 ^17.1 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] 18.0 ^18.1 Efficiently Organic: Researchers Use Pentacene To Develop Next-generation Solar Power sciencedaily.com Link （頁面存檔備份，存於網際網路檔案館）

[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] 20.0 ^20.1 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] 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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