Tuesday, April 16, 2019

organic chemistry - Is [7]сirculene aromatic or anti-aromatic?


This compound is called [7]circulene and is one of the examples of non-planar aromatic systems (1). From the first overview of this compound, it is observed that there are 7 benzene rings so one would conclude that it is an aromatic compound:


7 circulene


There are $7 \times 4 = 28$ $\pi$-electrons, so this compound satisfies the criteria of anti-aromacity. Then how come this compound is aromatic?


(1) Smith, M. March’s advanced organic chemistry: reactions, mechanisms, and structure, 7th ed.; Wiley: Hoboken, New Jersey, 2013, p. 48, compound 40.




Answer




TL;DR: We don't count $\pi$ electrons here, but the $\pi$ conjugated circuits (1). [7]-сirculene has all conjugated circles of size $4n + 2$, and none of $2n$, what makes it an aromatic compound.



Strictly speaking, the aromaticity $4n + 2$ and antiaromaticity $4n$ rules in their original interpretation are very limited and cannot be universally applied:


According to the original Hückel $4n + 2$ rule, if a monocyclic, planar molecule has $4n + 2$ $\pi$ electrons, it is considered aromatic.


But the count of $\pi$ electrons is not what matters for polycyclic compounds, therefore a generalized $4n + 2$ rule exists: if a conjugated molecule has only $4n + 2$ $\pi$ conjugated circuits, it is considered aromatic.


Non-benzenoid compounds can have both $4n + 2$ as well as $4n$ number of conjugated circuits counted by taking into account all Kekule structures. Among non-benzenoid non-alternant polycyclic hydrocarbons [5]-сirculene and [7]-сirculene both have only $4n + 2$ ($6, 10, 14, ...$) numbers of circuits.


(1) Gutman, I.; Cyvin, S. J. Journal of Molecular Structure: THEOCHEM 1989, 184 (1), 159–163.


Also, check out this question regarding pyrene.



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