Of graphs and graphenes: molecular design and chemical studies of aromatic compounds

In general, the term ‘aromatic’ indicates a pleasant smell or fragrance from fresh flowers, freshly prepared coffee, etc. In the early history of organic chemistry, many benzene derivatives were isolated from the pleasant odor oils of the plants. For example, vanillin was isolated from the oil of vanilla, methyl salicylate from the oil of wintergreen, and cinnamaldehyde from the oil of cinnamon. They all had a pleasant odor; hence the name aromatic was given.
In 1825, Faraday isolated benzene...

Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom, respectively.

Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH2 group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH2 group is sp3 hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.
Due to the absence of continuous overlap of p...

The inscribed polygon method is consistent with Hückel’s 4n + 2 rule and helps to learn whether the given cyclic compound is aromatic or not. The compound is stable and aromatic if every bonding molecular orbital (MO) is completely filled with a pair of electrons. However, if the non-bonding or antibonding orbitals are filled with electrons, the compound is unstable and not aromatic. Consider the Frost circle diagrams for cycloalkenes containing 4 to 8 carbons.

Aromatic compounds can be identified or analyzed using proton NMR and carbon‐13 NMR. Typically, aromatic hydrogens or hydrogens directly bonded to the aromatic rings are strongly deshielded by the aromatic ring current. Therefore, they absorb in the range of 6.5–8.0 ppm in proton NMR spectra. For instance, aromatic hydrogens directly bonded to the benzene ring absorb at 7.3 ppm. However, aromatic hydrogens of larger rings absorb farther upfield or downfield than the ideal range. Consider...

Like benzene, cyclobutadiene and cyclooctatetraene are cyclic compounds with alternate single and double bonds. However, their chemical behavior differs from benzene, as they are unstable and not aromatic. So, what are the structural characteristics of unsaturated compounds categorized as aromatic?
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.