Aromaticity is a chemical property in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibit a stabilization stronger than would be expected by the stabilization of conjugation alone. It can also be considered a manifestation of cyclic delocalization and of resonance.
This is usually considered to be because electrons are free to cycle around circular arrangements of atoms, which are alternately single- and double-bonded to one another. These bonds may be seen as a hybrid of a single bond and a double bond, each bond in the ring identical to every other. This commonly-seen model of aromatic rings, namely the idea that benzene was formed from a six-membered carbon ring with alternating single and double bonds (cyclohexatriene), was developed by Kekulé (see "History" section below). The model for benzene consists of two resonance forms, which corresponds to the double and single bonds' switching positions. Benzene is a more stable molecule than would be expected without accounting for charge delocalization.
A better representation is that of the circular π bond (Armstrong's inner cycle), in which the electron density is evenly distributed through a π bond above and below the ring. This model more correctly represents the location of electron density within the aromatic ring.
The single bonds are formed with electrons in line between the carbon nuclei—these are called sigma bonds. Double bonds consist of a sigma bond and a π bond. The π-bonds are formed from overlap of atomic p-orbitals above and below the plane of the ring. The following diagram shows the positions of these p-orbitals:
Since they are out of the plane of the atoms, these orbitals can interact with each other freely, and become delocalised. This means that instead of being tied to one atom of carbon, each electron is shared by all six in the ring. Thus, there are not enough electrons to form double bonds on all the carbon atoms, but the "extra" electrons strengthen all of the bonds on the ring equally. The resulting molecular orbital has π symmetry.
The cyclohexatriene structure for benzene was first proposed by August Kekulé in 1865. Over the next few decades, most chemists readily accepted this structure, since it accounted for most of the known isomeric relationships of aromatic chemistry. However, it was always puzzling that this purportedly highly-unsaturated molecule was so unreactive toward addition reactions.
The discoverer of the electron J. J. Thomson, in 1921 placed three equivalent electrons between each carbon atom in benzene.
An explanation for the exceptional stability of benzene is conventionally attributed to Sir Robert Robinson, who was apparently the first (in 1925) to coin the term aromatic sextet as a group of six electrons that resists disruption.
In fact, this concept can be traced further back, via Ernest Crocker in 1922, to Henry Edward Armstrong, who in 1890, in an article entitled The structure of cycloid hydrocarbons, wrote the (six) centric affinities act within a cycle...benzene may be represented by a double ring (sic) ... and when an additive compound is formed, the inner cycle of affinity suffers disruption, the contiguous carbon-atoms to which nothing has been attached of necessity acquire the ethylenic condition.
Here, Armstrong is describing at least four modern concepts. First, his "affinity" is better known nowadays as the electron, which was only to be discovered seven years later by J. J. Thomson. Second, he is describing electrophilic aromatic substitution, proceeding (third) through a Wheland intermediate, in which (fourth) the conjugation of the ring is broken. He introduced the symbol C centered on the ring as a shorthand for the inner cycle, thus anticipating Eric Clar's notation. It is argued that he also anticipated the nature of wave mechanics, since he recognized that his affinities had direction, not merely being point particles, and collectively having a distribution that could be altered by introducing substituents onto the benzene ring (much as the distribution of the electric charge in a body is altered by bringing it near to another body).
Whereas benzene is aromatic (6 electrons, from 3 double bonds), cyclobutadiene is not, since the number of π delocalized electrons is 4, which of course is a multiple of 4. The cyclobutadienide (2−) ion, however, is aromatic (6 electrons). An atom in an aromatic system can have other electrons that are not part of the system, and are therefore ignored for the 4n + 2 rule. In furan, the oxygen atom is sp² hybridized. One lone pair is in the π system and the other in the plane of the ring (analogous to C-H bond on the other positions). There are 6 π electrons, so furan is aromatic.
Aromatic molecules typically display enhanced chemical stability, compared to similar non-aromatic molecules. A molecule that can be aromatic will tend to alter its electronic or conformational structure to be in this situation. This extra stability changes the chemistry of the molecule. Aromatic compounds undergo electrophilic aromatic substitution and nucleophilic aromatic substitution reactions, but not electrophilic addition reactions as happens with carbon-carbon double bonds.
Many of the earliest-known examples of aromatic compounds, such as benzene and toluene, have distinctive pleasant smells. This property led to the term "aromatic" for this class of compounds, and hence the term "aromaticity" for the eventually-discovered electronic property.
The circulating π electrons in an aromatic molecule produce ring currents that oppose the applied magnetic field in NMR. The NMR signal of protons in the plane of an aromatic ring are shifted substantially further down-field than those on non-aromatic sp² carbons. This is an important way of detecting aromaticity. By the same mechanism, the signals of protons located near the ring axis are shifted up-field. Aromatic molecules are able to interact with each other in so-called π-π stacking: the π systems form two parallel rings overlap in a "face-to-face" orientation. Aromatic molecules are also able to interact with each other in an "edge-to-face" orientation: the slight positive charge of the substituents on the ring atoms of one molecule are attracted to the slight negative charge of the aromatic system on another molecule.
Planar monocyclic molecules containing 4n π electrons are called antiaromatic and are, in general, destabilized. Molecules that could be antiaromatic will tend to alter their electronic or conformational structure to avoid this situation, thereby becoming non-aromatic. For example, cyclooctatetraene (COT) distorts itself out of planarity, breaking π overlap between adjacent double bonds.
Other aromatic compounds play key roles in the biochemistry of all living things. Three aromatic amino acids phenylalanine, tryptophan, and tyrosine, each serve as one the 20 basic building blocks of proteins. Further, all 5 nucleotides that make up the sequence of the genetic code in DNA are aromatic purines or pyrimidines. As well as that, the molecule haem contains an aromatic system with 22 π electrons. Chlorophyll also has a similar aromatic system.
A special case of aromaticity is found in homoaromaticity where conjugation is interrupted by a single sp³ hybridized carbon atom. When carbon in benzene is replaced by other elements in borabenzene, silabenzene, germanabenzene, stannabenzene, phosphorine or pyrylium salts the aromaticity is still retained. Aromaticity is also not limited to compounds of carbon, oxygen and nitrogen.
Metal aromaticity is believed to exist in certain metal clusters of aluminium. Möbius aromaticity occurs when a cyclic system of molecular orbitals formed from pπ atomic orbitals and populated in a closed shell by 4n (n is an integer) electrons is given a single half-twist to correspond to a Möbius topology. Because the twist can be left-handed or right-handed, the resulting Möbius aromatics are dissymmetric or chiral. Up to now there is no doubtless proof, that a Möbius aromatic molecule was synthesized. Aromatics with two half-twists corresponding to the paradromic topologies first suggested by Johann Listing have been proposed by Rzepa in 2005. In carbo-benzene the ring bonds are extended with alkyne and allene groups.