In Chapter 2 you saw how, if given the right amount of energy, electrons can be promoted from a low-energy atomic orbital to a higher energy one and how this gives rise to an atomic absorption spectrum. Exactly the same process can occur with molecular orbitals: energy of the right wavelength can promote an electron from a fi lled orbital (for example the HOMO) to an unfilled one (for example the LUMO), and plotting the absorption of energy against wavelength gives rise to a new type of spectrum called, for obvious reasons which you will see in a moment, a UV–visible spectrum. You have just seen that the energy difference between the HOMO and LUMO for butadiene is less than that for ethene. We would therefore expect butadiene to absorb light of longer wavelength than ethene (the longer the wavelength the lower the energy). This is indeed the case: butadiene absorbs at 215 nm compared to 185 nm for ethene. The conjugation in buta diene means it absorbs light of a longer wavelength than ethene. One of the consequences of conjugation is to lessen the gaps between fi lled and empty orbitals, and so allow absorption of light of a longer wavelength.

●The more conjugated a compound is, the smaller the energy transition between its HOMO and LUMO, and hence the longer the wavelength of light it can absorb. UV–visible spectroscopy can tell us about the conjugation present in a molecule.

 Both ethene and butadiene absorb in the UV region of the electromagnetic spectrum. If we extend the conjugation further, the gap between HOMO and LUMO will eventually be small enough to allow the compound to absorb visible light and hence have a colour. Lycopene, the pigment in tomatoes, which we introduced at the start of the chapter, has 11 conjugated double bonds (plus two unconjugated ones). It absorbs blue–green light at about 470 nm: consequently, tomatoes are red. Chlorophyll, in the margin, has a cyclic conjugated system: it absorbs at long wave lengths and is green.

مواضيع ذات صلة

? What makes benzene special

Aromaticity

Conjugation and reactivity: looking forward to Chapter 10

The amide group

Delocalization over three atoms is a common structural feature The carboxylate anion

The allyl system, The allyl anion

The colour of pigments depends on conjugation

The molecular orbitals of butadiene

Conjugation

Multiple double bonds not in a ring

Molecules with more than one C=C double bond Benzene has three strongly interacting double bonds

The structure of ethene (ethylene, CH2=CH2)