碗烯

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碗烯
IUPAC名
Dibenzo[ghi,mno]fluoranthene
别名 [5]circulene
识别
CAS号 5821-51-2
PubChem 11831840
ChemSpider 10006487
SMILES
InChI
InChIKey VXRUJZQPKRBJKH-UHFFFAOYAF
性质
化学式 C20H10
摩尔质量 250.29 g/mol g·mol⁻¹
若非注明,所有数据均出自一般条件(25 ℃,100 kPa)下。

碗烯Corannulene),又名心环烯,是一种多环芳香烃,化学式C20H10[1]由一个环戊烷周围并五个苯环组成,它具有碗状的空间结构,可看做是富勒烯C60的一个片段。在−64℃时,碗状结构翻转的能垒是42.7kJ/mol(10.2 kcal/mol)。[2]

合成[编辑]

通过快速真空裂解技术得到的碗烯纯度比溶液法低,但同时能得到各种碗烯衍生物。
1966年,碗烯首次由多步有机合成并从产物中分离出来。[3][4][5]的溴代衍生物在碱催化下通过分子内的亲核取代关环得四溴代的碗烯:

Corannulene synthesis Sygula 2000

再由过量的正丁基锂通过卤素-锂交换除溴,经水解得到碗烯。

有合成含不同官能团的碗烯衍生物的研究,例如含乙炔基,[2][6][7] 键,[8] 硫醚[9]官能团,[10]芳基,[11] 非那烯[12]的并环[13][14]的碗烯衍生物。

芳香性[编辑]

一种解释碗烯芳香性的模型将碗烯分成中间6电子和外围14电子的两个芳香性的共轭体系。这个模型由1966年首次合成碗烯的巴特和劳顿提出,[3]他们还给出了这个化合物的命名建议(corannulene意为核+轮烯)。

annulene-within-an-annulene model

然而,之后理论计算的结果并不支持这种模型。[15][16]

应用[编辑]

“球碳捕手”

碗烯被用于主客体化学的研究,例如碗烯基团与富勒烯[17][18]硝基苯之间的π重叠[19]

长脂肪烃基侧链取代碗烯存在热致变的六角形柱状液晶的中间相。[20]碗烯基团也被用于树形高分子的组装,[11]或研究其作为配体的性质。[21][22][23][24][25][26][27]乙炔基碗烯衍生物对于制造蓝光发射器有潜在的应用价值。[7]

参见[编辑]

参考文献[编辑]

  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  12. ^ Nishida, S.; Morita, Y.; Ueda, A.; Kobayashi, T.; Fukui, K.; Ogasawara, K.; Sato, K.; Takui, T. et al. 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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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.  编辑
  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