Forty years of Clar's aromatic π-sextet rule

Frontiers in Chemistry

Volumn 1, Issue , 2013, Pages

  Solà, Miquel ^a  

^a UNIVERSITY OF GIRONA   (Spain)

Author keywords

Benzenoid compounds; Clar's aromatic sextet rule; Graphene; Local aromaticity; Polycyclic aromatic hydrocarbons (PAHs)

Indexed keywords

EID: 84987629402     PISSN: None     EISSN: 22962646     Source Type: Journal    
DOI: 10.3389/fchem.2013.00022     Document Type: Review

References (75)

1. Aihara, J. (2002). Nucleus-independent chemical shifts and local aromaticities in large polycyclic aromatic hydrocarbons. Chem. Phys. Lett. 365, 34-39. doi: 10.1016/S0009-2614(02)01415-X
2. Altschuler, L., and Berliner, E. (1966). Rates of bromination of polynuclear aromatic hydrocarbons1. J. Am. Chem. Soc. 88, 5837-5845. doi: 10.1021/ja00976a027
3. Anusooya, Y., Chakrabarti, A., Pati, S. K., and Ramasesha, S. (1998). Ring currents in condensed ring systems. Int. J. Quant. Chem. 70, 503-513. doi: 10.1002/(SICI)1097-461X(1998)70:3<503::AID-QUA6>3.0.CO;2-Y
4. Armit, T. W., and Robinson, R. (1925). Polynuclear heterocyclic aromatic types. II. Some anhydronium bases. J. Chem. Soc. Trans. 127, 1604-1618. doi: 10.1039/ct9252701604
5. Balaban, A. T., and Klein, D. J. (2009). Claromatic carbon nanostructures. J. Phys. Chem. C 113, 19123-19133. doi: 10.1021/jp9082618
6. Bendikov, M., Duong, H. M., Starkey, K., Houk, K. N., Carter, E. A., and Wudl, F. (2004). Oligoacenes: theoretical prediction of open-shell singlet diradical ground states. J. Am. Chem. Soc. 126, 7416-7417. doi: 10.1021/ja048919w
7. Berresheim, A. J., Müller, M., and Müllen, K. (1999). Polyphenylene nanostructures. Chem. Rev. 99, 1747-1786. doi: 10.1021/cr970073+
8. Biermann, D., and Schmidt, W. (1980). Diels-Alder reactivity of polycyclic aromatic hydrocarbons. 1. Acenes and benzologs. J. Am. Chem. Soc. 102, 3163-3173. doi: 10.1021/ja00529a046
9. Bühl, M., and van Wüllen, C. (1995). Computational evidence for a new C84 isomer. Chem. Phys. Lett. 247, 63-68. doi: 10.1016/0009-2614(95)01193-6
10. Chen, T.-A., and Liu, R.-S. (2011). Synthesis of polyaromatic hydrocarbons from bis(biaryl)diynes: large PAHs with low Clar sextets. Chemistry 17, 8023-8027. doi: 10.1002/chem.201101057
11. Chen, Z., Wannere, C. S., Corminboeuf, C., Puchta, R., and Schleyer, P. V. R. (2005). Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem. Rev. 105, 3842-3888. doi: 10.1021/cr030088+
12. Cheng, M.-F., and Li, W.-K. (2003). A computational study of the Diels-Alder reactions involving acenes: reactivity and aromaticity. Chem. Phys. Lett. 368, 630-638. doi: 10.1016/S0009-2614(02)01955-3
13. Chien, S.-H., Cheng, M.-F., Lau, K.-C., and Li, W.-K. (2005). Theoretical study of the Diels-Alder reactions between singlet (1δg) oxygen and acenes. J. Phys. Chem. A 109, 7509-7518. doi: 10.1021/jp0503009
14. Ciesielski, A., Krygowski, T. M., and Cyranski, M. K. (2008). Why are the kinked polyacenes more stable than the straight ones? A topological study and introduction of a new topological index of aromaticity. J. Chem. Inf. Model. 48, 1358-1366. doi: 10.1021/ci800061q
15. Clar, E. (1964). Polycyclic Hydrocarbons. London: Academic.
16. Clar, E. (1972). The Aromatic Sextet. New York, NY: Wiley.
17. Clar, E., and Zander, M. (1958). 1,12,2,3,10,11-Tribenzoperylene. J. Chem. Soc. 1861-1865. doi: 10.1039/jr9580001861
18. Cyranski, M. C., Stepién, B. T., and Krygowski, T. M. (2000). Global and local aromaticity of linear and angular polyacenes. Tetrahedron 56, 9663-9967. doi: 10.1016/S0040-4020(00)00919-4
19. Dabestani, R., and Ivanov, I. N. (1999). A compilation of physical, spectroscopic and photophysical properties of polycyclic aromatic hydrocarbons. Photochem. Photobiol. 70, 10-34. doi: 10.1111/j.1751-1097.1999.tb01945.x
20. Dias, J. R. (2004). The most stable class of benzenoid hydrocarbons-new topological correlations of strain-free total resonant sextet benzenoids. J. Chem. Inf. Comput. Sci. 44, 1210-1220. doi: 10.1021/ci049910g
21. Dominikowska, J., and Palusiak, M. (2011). Does the concept of Clar's aromatic sextet work for dicationic forms of polycyclic aromatic hydrocarbons?-testing the model against charged systems in singlet and triplet states. Phys. Chem. Chem. Phys. 13, 11976-11984. doi: 10.1039/c1cp20530g
22. Dötz, F., Brand, J. D., Ito, S., Gherghel, L., and Müllen, K. (2000). Synthesis of large polycyclic aromatic hydrocarbons: variation of size and periphery. J. Am. Chem. Soc. 122, 7707-7717. doi: 10.1021/ja000832x
23. Einholz, R., and Bettinger, H. F. (2013). Heptacene: increased persistence of a 4n+2 p-electron polycyclic aromatic hydrocarbon by oxidation to the 4np-electron dication. Angew. Chem. Int. Ed. Engl. 52, 9818-9820. doi: 10.1002/anie.201209722
24. Feixas, F., Matito, E., Poater, J., and Solà, M. (2008). On the performance of some aromaticity indices: a critical assessment using a test set. J. Comput. Chem. 29, 1543-1554. doi: 10.1002/jcc.20914
25. Glidewell, C., and Lloyd, D. (1984). MNDO study of bond orders in some conjugated bi-and tri-cyclic hydrocarbons. Tetrahedron 40, 4455-4472. doi: 10.1016/S0040-4020(01)98821-0
26. Gross, L., Mohn, F., Moll, N., Schuler, B., Criado, A., Guitián, E., et al. (2012). Bond-order discrimination by atomic force microscopy. Science 337, 1326-1329. doi: 10.1126/science.1225621
27. Güell, M., Poater, J., Luis, J. M., Mó, O., Yáñez, M., and Solà, M. (2005). An aromaticity analysis of lithium-cation/p complexes of aromatic systems. Chemphyschem 6, 2552-2561. doi: 10.1002/cphc.200500216
28. Gutman, I., and Babic, D. (1991). Characterization of all-benzenoid hydrocarbons. J. Mol. Struct. (Theochem) 251, 367-373. doi: 10.1016/0166-1280(91)85159-5
29. Gutman, I., Tomovic, Ž., Müllen, K., and Rabe, J. P. (2004). On the distribution of p-electrons in large polycyclic aromatic hydrocarbons. Chem. Phys. Lett. 397, 412-416. doi: 10.1016/j.cplett.2004.08.138
30. Havenith, R. W. A., Van Lenthe, J. H., Dijkstra, F., and Jenneskens, L. W. (2001). Aromaticity of pyrene and its cyclopentafused congeners-resonance and NICS criteria. An ab initio valence bond analysis in terms of Kekule resonance structures. J. Phys. Chem. A 105, 3838-3845. doi: 10.1021/jp003344k
31. Hückel, E. (1931a). Quanstentheoretische Beiträge zum Benzolproblem II. Quantentheorie der induzierten Polaritäten. Z. Physik 72, 310-337. doi: 10.1007/BF01341953
32. Hückel, E. (1931b). Quantentheoretische Beiträge zum Benzolproblem I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen. Z. Physik 70, 104-186.
33. Hückel, E. (1932). Quantentheoretische Beiträge zum Problem der Aromatischen und Ungesättigten Verbindungen. III. Z. Physik 76, 628-648. doi: 10.1007/BF01341936
34. Hückel, E. (1937). The theory of unsaturated and aromatic compounds. Z. Elektrochemie 43, 752-788, 827-849
35. Ito, S., Herwig, P. T., Böhme, T., Rabe, J. P., Rettig, W., and Müllen, K. (2000). Bishexa-peri-hexabenzocoronenyl: a "Superbiphenyl". J. Am. Chem. Soc. 122, 7698-7706. doi: 10.1021/ja000850e
36. Iyer, V. S., Yoshimura, K., Enkelmann, V., Epsch, R., Rabe, J. P., and Müllen, K. (1998). A soluble C60 graphite segment. Angew. Chem. Int. Ed. 37, 2696-2699. doi: 10.1002/(SICI)1521-3773(19981016)37:19<2696::AID-ANIE2696>3.0.CO;2-E
37. Jiménez-Halla, J. O. C., Robles, J., and Solà, M. (2008). Coordination of bis(tricarbonylchromium) complexes to small polycyclic aromatic hydrocarbons: structure, relative stabilities, and bonding. Chem. Phys. Lett. 465, 181-189. doi: 10.1016/j.cplett.2008.10.001
38. Kay, M. I., Okaya, Y., and Cox, D. E. (1971). A refinement of the structure of the room-temperature phase of phenanthrene, C14H10, from X-ray and neutron diffraction data. Acta Cryst. Sec. B 27, 26-33. doi: 10.1107/S0567740871001663
39. Kruszewski, J., and Krygowski, T. M. (1972). Definition of aromaticity basing on the harmonic oscillator model. Tetrahedron Lett. 13, 3839-3842. doi: 10.1016/S0040-4039(01)94175-9
40. Krygowski, T. M. (1993). Crystallographic studies of inter-and intra-molecular interactions reflected in benzenoid hydrocarbons. nonequivalence of indices of aromaticity. J. Chem. Inf. Comp. Sci. 33, 70-78. doi: 10.1021/ci00011a011
41. Krygowski, T. M., Cyrañski, M. K., Czarnocki, Z., Häfelinger, G., and Katritzky, A. R. (2000). Aromaticity: a theoretical concept of immense practical importance. Tetrahedron 56, 1783-1796. doi: 10.1016/S0040-4020(99)00979-5
42. Kumar, B., Viboh, R. L., Bonifacio, M. C., Thompson, W. B., Buttrick, J. C., Westlake, B. C., et al. (2012). Septulene: the heptagonal homologue of kekulene. Angew. Chem. Int. Ed. Engl. 51, 12795-12800. doi: 10.1002/anie.201203266
43. Ligabue, A., Pincelli, U., Lazzeretti, P., and Zanasi, P. (1999). Current density maps, magnetizability, and nuclear magnetic shielding tensors for anthracene, phenanthrene and triphenylene. J. Am. Chem. Soc. 121, 5513-5518. doi: 10.1021/ja9900656
44. Martín-Martínez, F. J., Fias, S., Van Lier, G., De Proft, F., and Geerlings, P. (2012). Electronic structure and aromaticity of graphene nanoribbons. Chemistry 18, 6183-6194. doi: 10.1002/chem.201103977
45. Martín-Martínez, F. J., Fias, S., Van Lier, G., De Proft, F., and Geerlings, P. (2013). Tuning aromaticity patterns and electronic properties of armchair graphene nanoribbons with chemical edge functionalisation. Phys. Chem. Chem. Phys. 15, 12637-12647. doi: 10.1039/c3cp51293b
46. Martín-Martínez, F. J., Melchor, S., and Dobado, J. A. (2008). Clar-Kekulé structuring in armchair carbon nanotubes. Org. Lett. 10, 1991-1994. doi: 10.1021/ol800587s
47. Matito, E., Duran, M., and Solà, M. (2005). The Aromatic Fluctuation Index (FLU): a new aromaticity index based on electron delocalization. J. Chem. Phys. 122:014109. doi: 10.1063/1.1824895
48. Moran, D., Stahl, F., Bettinger, H. F., Schaefer, H. F., and Schleyer, P. V. R. (2003). Towards graphite: magnetic properties of large polybenzenoid hydrocarbons. J. Am. Chem. Soc. 125, 6746-6752. doi: 10.1021/ja034497z
49. Palusiak, M., Simon, S., and Solà, M. (2006). Interplay between intramolecular resonance-assisted hydrogen bonding and aromaticity in o-hydroxyaryl aldehydes. J. Org. Chem. 71, 5241-5248. doi: 10.1021/jo060591x
50. Palusiak, M., Simon, S., and Solá, M. (2009). Interplay between intramolecular resonance-assisted hydrogen bonding and local aromaticity. II. 1,3-Dihydroxyaryl-2-aldehydes. J. Org. Chem. 74, 2059-2066. doi: 10.1021/jo802498h
51. Poater, J., Bofill, J. M., Alemany, P., and Solà, M. (2005). Local aromaticity of the lowest-lying singlet states of [n]acenes (n = 6-9). J. Phys. Chem. A 109, 10629-10632. doi: 10.1021/jp055188t
52. Poater, J., Fradera, X., Duran, M., and Solà, M. (2003). The delocalization index as an electronic aromaticity criterion. application to a series of planar polycyclic aromatic hydrocarbons. Chem. Eur. J. 9, 400-406. doi: 10.1002/chem.200390041
53. Poater, J., Visser, R., Solà, M., and Bickelhaupt, F. M. (2007). Polycyclic benzenoids. Why kinked is more stable than straight. J. Org. Chem. 72, 1134-1142. doi: 10.1021/jo061637p
54. Portella, G., Poater, J., Bofill, J. M., Alemany, P., and Solà, M. (2005). Local aromaticity of [n]acenes, [n]phenacenes, and [n]helicenes (n = 1-9). J. Org. Chem. 70, 2509-2521. doi: 10.1021/jo0480388
55. Randic, M. (2003). Aromaticity of polycyclic conjugated hydrocarbons. Chem. Rev. 103, 3449-3605. doi: 10.1021/cr9903656
56. Ruiz-Morales, Y. (2004). The agreement between Clar structures and nucleus-independent chemical shift values in pericondensed benzenoid polycyclic aromatic hydrocarbons: an application of the Y-Rule. J. Phys. Chem. A 108, 10873-10896. doi: 10.1021/jp040179q
57. Samorí, P., Fechtenkötter, A., Jäckel, F., Böhme, T., Müllen, K., and Rabe, J. P. (2001). Supramolecular staircase via self-assembly of disklike molecules at the solid-liquid interface. J. Am. Chem. Soc. 123, 11462-11467. doi: 10.1021/ja0111380
58. Samorí, P., Severin, N., Simpson, C. D., Müllen, K., and Rabe, J. P. (2002). Epitaxial composite layers of electron donors and acceptors from very large polycyclic aromatic hydrocarbons. J. Am. Chem. Soc. 124, 9454-9457. doi: 10.1021/ja020323q
59. Sarova, G. H., and Berberan-Santos, M. N. (2004). Kinetics of the Diels-Alder reaction between C60 and acenes. Chem. Phys. Lett. 397, 402-407. doi: 10.1016/j.cplett.2004.09.005
60. Schleyer, P. V. R., Maerker, C., Dransfeld, A., Jiao, H., and Van Eikema Hommes, N. J. R. (1996). Nucleus-independent chemical shifts: a simple and efficient aromaticity probe. J. Am. Chem. Soc. 118, 6317-6318. doi: 10.1021/ja960582d
61. Schleyer, P. V. R., Manoharan, M., Jiao, H. J., and Stahl, F. (2001). The acenes: is there a relationship between aromatic stabilization and reactivity? Org. Lett. 3, 3643-3646. doi: 10.1021/ol016553b
62. Schulman, J. M., and Disch, R. L. (1999). Aromatic character of [n]helicenes and [n]phenacenes. J. Phys. Chem. A 103, 6669-6672. doi: 10.1021/jp9910587
63. Sobczyk, L., Grabowski, S. J., and Krygowski, T. M. (2005). Interrelation between H-Bond and Pi-electron delocalization. Chem. Rev. 105, 3513-3560. doi: 10.1021/cr030083c
64. Solà, M., Feixas, F., Jiménez-Halla, J. O. C., Matito, E., and Poater, J. (2010). A critical assessment of the performance of magnetic and electronic indices of aromaticity. Symmetry 2, 1156-1179. doi: 10.3390/sym2021156
65. Steiner, E., and Fowler, P. W. (1996). Ring currents in aromatic hydrocarbons. Int. J. Quant. Chem. 60, 609-616. doi: 10.1002/(SICI)1097-461X(1996)60:1<609::AID-QUA58>3.0.CO;2-1
66. Steiner, E., Fowler, P. W., and Havenith, R. W. A. (2002a). Current densities of localized and delocalized electrons in molecules. J. Phys. Chem. A 106, 7048-7056. doi: 10.1021/jp020819u
67. Steiner, E., Fowler, P. W., Jenneskens, L. W., and Havenith, R. W. A. (2002b). Local and global paratropic and diatropic ring currents in pyrene and its cyclopenta-fused congeners. Eur. J. Org. Chem. 2002, 163-169. doi: 10.1002/1099-0690(20021)2002:1<163::AID-EJOC163>3.0.CO;2-3
68. Steiner, E., Fowler, P. W., and Jenneskens, L. W. (2001). Counter-rotating ring currents in coronene and corannulene. Angew. Chem. Int. Ed. Engl. 40, 362-366. doi: 10.1002/1521-3773(20010119)40:2<362::AID-ANIE362>3.3.CO;2-Q
69. Steiner, E., Fowler, P. W., Soncini, A., and Jenneskens, L. W. (2007). Current-density maps as probes of aromaticity: global and Clar p ring currents in totally resonant polycyclic aromatic hydrocarbons. Faraday Discuss. 135, 309-323. doi: 10.1039/b604769f
70. Suresh, C. H., and Gadre, S. R. (1999). Clar's aromatic sextet theory revisited via molecular electrostatic potential topography. J. Org. Chem. 64, 2505-2512. doi: 10.1021/jo990050q
71. Wassmann, T., Seitsonen, A. P., Saitta, A. M., Lazzeri, M., and Mauri, F. (2010). Clar's theory, p-electron distribution, and geometry of graphene nanoribbons. J. Am. Chem. Soc. 132, 3440-3451. doi: 10.1021/ja909234y
72. Watson, M. D., Jäckel, F., Severin, N., Rabe, J. P., and Müllen, K. (2004). A Hexa-peri-hexabenzocoronene Cyclophane: an addition to the toolbox for molecular electronics. J. Am. Chem. Soc. 126, 1402-1407. doi: 10.1021/ja037520p
73. Wiberg, K. B. (1997). Properties of some condensed aromatic systems. J. Org. Chem. 62, 5720-5727. doi: 10.1021/jo961831j
74. Wiberg, K. B. (1999). "Pauling's legacy: modern modelling of the chemical bond," in Theoretical and Computational Chemistry, eds Z. B. Maksic and W. J. Orville-Thomas (Amsterdam: Elsevier), 519-536. doi: 10.1016/S1380-7323(99)80021-1
75. Yoshida, M., and Aihara, J. (1999). Validity of the weighted HOMO-LUMO energy separation as an index of kinetic stability for fullerenes with up to 120 carbon atoms. Phys. Chem. Chem. Phys. 1, 227-230. doi: 10.1039/a807917j