碗烯

心環烯
IUPAC名
Dibenzo[ghi,mno]fluoranthene
別名 [5]circulene
識別
CAS號 5821-51-2
PubChem 11831840
ChemSpider 10006487
SMILES
InChI
InChIKey VXRUJZQPKRBJKH-UHFFFAOYAF
性質
化學式 C20H10
摩爾質量 250.29 g/mol g·mol⁻¹
若非註明,所有數據均出自一般條件(25 ℃,100 kPa)下。

心環烯Corannulene),又名碗烯,是一種多環芳香烴,化學式C20H10[1]由一個環戊烷周圍並五個苯環組成,它具有碗狀的空間結構,可看做是富勒烯C60的一個片段。在−64℃時,碗狀結構翻轉的能壘是42.7kJ/mol(10.2 kcal/mol)。[2]

合成

通過快速真空裂解技術得到的碗烯純度比溶液法低,但同時能得到各種碗烯衍生物。
1966年,碗烯首次由多步有機合成並從產物中分離出來。[3][4][5]由熒的溴代衍生物在鹼催化下通過分子內的親核取代關環得四溴代的碗烯:

Corannulene synthesis Sygula 2000 

再由過量的正丁基鋰通過鹵素-鋰交換除溴,經水解得到碗烯。

有合成含不同官能團的碗烯衍生物的研究,例如含乙炔基,[2][6][7] 鍵,[8] 硫醚[9]官能團,[10]芳基,[11] 非那烯[12]的並環[13][14]的碗烯衍生物。

芳香性

一種解釋碗烯芳香性的模型將碗烯分成中間6電子和外圍14電子的兩個芳香性的共軛體系。這個模型由1966年首次合成碗烯的巴特和勞頓提出,[3]他們還給出了這個化合物的命名建議(corannulene意為核+輪烯)。

annulene-within-an-annulene model 

然而,之後理論計算的結果並不支持這種模型。[15][16]

應用

 
「球碳捕手」

碗烯被用於主客體化學的研究,例如碗烯基團與富勒烯[17][18]硝基苯之間的π重疊[19]

長脂肪烴基側鏈取代碗烯存在熱致變的六角形柱狀液晶的中間相。[20]碗烯基團也被用於樹形高分子的組裝,[11]或研究其作為配體的性質。[21][22][23][24][25][26][27]乙炔基碗烯衍生物對於製造藍光發射器有潛在的應用價值。[7]

參見

參考文獻

  1. ^ Scott, L. T.; Bronstein, H. E.; Preda, D. V.; Ansems, R. B. M.; Bratcher, M. S.; Hagen, S. Geodesic polyarenes with exposed concave surfaces. Pure and Applied Chemistry. 1999, 71 (2): 209. doi:10.1351/pac199971020209. 
  2. ^ 2.0 2.1 Scott, L. T.; Hashemi, M. M.; Bratcher, M. S. Corannulene bowl-to-bowl inversion is rapid at room temperature. Journal of the American Chemical Society. 1992, 114 (5): 1920. doi:10.1021/ja00031a079. 
  3. ^ 3.0 3.1 Barth, W. E.; Lawton, R. G. Journal of the American Chemical Society. 1966, 88 (2): 380. doi:10.1021/ja00954a049. 
  4. ^ Scott, L. T.; Hashemi, M. M.; Meyer, D. T.; Warren, H. B. Corannulene. A convenient new synthesis. Journal of the American Chemical Society. 1991, 113 (18): 7082. doi:10.1021/ja00018a082. 
  5. ^ Sygula, A.; Rabideau, P. W. A Practical, Large Scale Synthesis of the Corannulene System. Journal of the American Chemical Society. 2000, 122 (26): 6323. doi:10.1021/ja0011461. 
  6. ^ Wu, Y.; Bandera, D.; Maag, R.; Linden, A.; Baldridge, K.; Siegel, J. Multiethynyl corannulenes: synthesis, structure, and properties. Journal of the American Chemical Society. 2008, 130 (32): 10729–10739. doi:10.1021/ja802334n. PMID 18642812. 
  7. ^ 7.0 7.1 Mack, J.; Vogel, P.; Jones, D.; Kaval, N.; Sutton, A. The development of corannulene-based blue emitters. Organic & biomolecular chemistry. 2007, 5 (15): 2448–2452. doi:10.1039/b705621d. PMID 17637965. 
  8. ^ Gershoni-Poranne, R.; Pappo, D.; Solel, E.; Keinan, E. Corannulene ethers via Ullmann condensation. Organic Letters. 2009, 11 (22): 5146–5149. doi:10.1021/ol902352k. PMID 19905024. 
  9. ^ Baldridge, K.; Hardcastle, K.; Seiders, T.; Siegel, J. Synthesis, structure and properties of decakis(phenylthio)corannulene. Organic & biomolecular chemistry. 2010, 8 (1): 53–55. doi:10.1039/b919616a. PMID 20024131. 
  10. ^ Choi, H.; Kim, C.; Park, K. M.; Kim, J.; Kang, Y.; Ko, J. Synthesis and structure of penta-platinum σ-bonded derivatives of corannulene. Journal of Organometallic Chemistry. 2009, 694 (22): 3529. doi:10.1016/j.jorganchem.2009.07.015. 
  11. ^ 11.0 11.1 Pappo, D.; Mejuch, T.; Reany, O.; Solel, E.; Gurram, M.; Keinan, E. Diverse Functionalization of Corannulene: Easy Access to Pentagonal Superstructure. Organic Letters. 2009, 11 (5): 1063–1066. doi:10.1021/ol8028127. PMID 19193048. 
  12. ^ Nishida, S.; Morita, Y.; Ueda, A.; Kobayashi, T.; Fukui, K.; Ogasawara, K.; Sato, K.; Takui, T.; Nakasuji, K. Curve-structured phenalenyl chemistry: synthesis, electronic structure, and bowl-inversion barrier of a phenalenyl-fused corannulene anion. Journal of the American Chemical Society. 2008, 130 (45): 14954–14955. doi:10.1021/ja806708j. PMID 18937470. 
  13. ^ Steinberg, B.; Jackson, E.; Filatov, A.; Wakamiya, A.; Petrukhina, M.; Scott, L. Aromatic pi-systems more curved than C(60). The complete family of all indenocorannulenes synthesized by iterative microwave-assisted intramolecular arylations. Journal of the American Chemical Society. 2009, 131 (30): 10537–10545. doi:10.1021/ja9031852. PMID 19722628. 
  14. ^ Corannulenylferrocenes: towards a 1D, non-covalent metal–organic nanowire Berit Topolinski , Bernd M. Schmidt , Michael Kathan , Sergej I. Troyanov and Dieter Lentz Chem. Commun., 2012,48, 6298-6300 doi:10.1039/C2CC32275G
  15. ^ Sygula, A. Structure and inversion barriers of corannulene, its dianion and tetraanion. An ab initio study. Journal of Molecular Structure: THEOCHEM. 1995, 333: 215–226. doi:10.1016/0166-1280(94)03961-J. 
  16. ^ Monaco, G.; Scott, L.; Zanasi, R. Magnetic euripi in corannulene. The journal of physical chemistry. A. 2008, 112 (35): 8136–8147. doi:10.1021/jp8038779. PMID 18693706. 
  17. ^ Sygula, A.; Fronczek, F.; Sygula, R.; Rabideau, P.; Olmstead, M. A double concave hydrocarbon buckycatcher. Journal of the American Chemical Society. 2007, 129 (13): 3842–3843. doi:10.1021/ja070616p. PMID 17348661. 
  18. ^ Wong, B. M. Noncovalent interactions in supramolecular complexes: a study on corannulene and the double concave buckycatcher. Journal of computational chemistry. 2009, 30 (1): 51–56. doi:10.1002/jcc.21022. PMID 18504779. 
  19. ^ Kobryn, L.; Henry, W. P.; Fronczek, F. R.; Sygula, R.; Sygula, A. Molecular clips and tweezers with corannulene pincers. Tetrahedron Letters. 2009, 50 (51): 7124. doi:10.1016/j.tetlet.2009.09.177. 
  20. ^ Miyajima, D.; Tashiro, K.; Araoka, F.; Takezoe, H.; Kim, J.; Kato, K.; Takata, M.; Aida, T. Liquid crystalline corannulene responsive to electric field. Journal of the American Chemical Society. 2009, 131 (1): 44–45. doi:10.1021/ja808396b. PMID 19128171. 
  21. ^ Hexahapto Metal Coordination to Curved Polyaromatic Hydrocarbon Surfaces: The First Transition Metal Corannulene Complex T. Jon Seiders, Kim K. Baldridge, Joseph M. O'Connor, and Jay S. Siegel J. Am. Chem. Soc., 1997, 119 (20), pp 4781–4782 doi:10.1021/ja964380t
  22. ^ d8 Rhodium and Iridium Complexes of Corannulene Jay S. Siegel, Kim K. Baldridge, Anthony Linden, and Reto Dorta J. Am. Chem. Soc., 2006, 128 (33), pp 10644–10645 doi:10.1021/ja062110x
  23. ^ Petrukhina, Marina A. Coordination of buckybowls: the first concave-bound metal complex. Angewandte Chemie (International ed. in English). 2008, 47 (9): 1550–1552. doi:10.1002/anie.200704783. PMID 18214869. 
  24. ^ Zhu, B.; Ellern, A.; Sygula, A.; Sygula, R.; Angelici, R. J. η6-Coordination of the Curved Carbon Surface of Corannulene (C20H10) to (η6-arene)M2+(M = Ru, Os). Organometallics. 2007, 26 (7): 1721. doi:10.1021/om0610795. 
  25. ^ Petrukhina, M. A.; Sevryugina, Y.; Rogachev, A. Y.; Jackson, E. A.; Scott, L. T. Corannulene:  A Preference forexo-Metal Binding. X-ray Structural Characterization of [Ru2(O2CCF3)2(CO)4·(η2-C20H10)2]. Organometallics. 2006, 25 (22): 5492. doi:10.1021/om060350f. 
  26. ^ Siegel, J.; Baldridge, K.; Linden, A.; Dorta, R. D8 rhodium and iridium complexes of corannulene. Journal of the American Chemical Society. 2006, 128 (33): 10644–10645. doi:10.1021/ja062110x. PMID 16910635. 
  27. ^ Bandera, D., Baldridge, K. K., Linden, A., Dorta, R. and Siegel, J. S. (2011), Stereoselective Coordination of C5-Symmetric Corannulene Derivatives with an Enantiomerically Pure [RhI(nbd*)] Metal Complex. Angewandte Chemie International Edition, 50: 865–867. doi:10.1002/anie.201006877