14.

2 Absorption Spectra
of Alkenes and Aromatics

• spectral data for linear polyenes

• spectral data for linear, fused aromatics
• spectral data for non-linear, fused
aromatics
• spectral data for linear polyphenyls
• quite often the absorption spectrum of a
new compound can be estimated by
comparison to known analogs

14.2 : 1/8
 Linear Polyenes

CH CH
n
n name λmax (nm) εmax (M-1 cm-1)
1 ethylene 163 ?
2 butadiene 217 21,000
3 hexatriene 268 35,000
4 octatetraene 304 ?
5 decapentaene 328 120,000

• as the number of double bonds increases, the long wavelength

absorption shifts to higher values (called a red-shift)
• the molar absorptivity increases as the molecular orbital size
increases
• to anticipate the spectrum, use the number of conjugated double
bonds, i.e. CH2=CH-CH2-CH=CH2 has a spectrum closer to
ethylene than butadiene.

14.2 : 2/8
 Linear Fused Aromatics (1)

structure name λmax (nm) εmax (M-1 cm-1)

benzene 255 220

naphthalene 315 320

anthracene 357 10,000

tetracene 471 10,000

• as the number of fused rings increases, the long wavelength

absorption shifts to higher values
• the long wavelength transition is forbidden in benzene and
naphthalene, but allowed in anthracene and tetracene
• to anticipate the spectrum use the number of conjugated double
bonds, i.e. diphenylmethane has a spectrum that resembles
toluene
14.2 : 3/8
 Linear Fused Aromatics (2)

14.2 : 4/8 R. A. Freidel and M. Orchin, Ultraviolet Spectra of Aromatic Compounds, Wiley, New York, 1951.
 Non-Linear Fused Aromatics (1)

structure name 0-0 band (nm) ε0-0 (M-1 cm-1)

3,4-benzo
370 170
phenanthrene

chrysene 360 800

pyrene 370 120

perylene 437 37,000

• the 0-0 band appears at lower wavelengths than would be

predicted by the number of fused rings (379 for anthracene and
479 for tetracene)
• the first three have band positions similar to anthracene and
molar absorptivities similar to naphthalene
• perylene has properties between anthracene and tetracene
14.2 : 5/8
 Non-Linear Fused Aromatics (2)

14.2 : 6/8 R. A. Freidel and M. Orchin, Ultraviolet Spectra of Aromatic Compounds, Wiley, New York, 1951.
 Linear Polyphenyls (1)

n name 0-0 band (nm) λmax(nm) εmax (M-1 cm-1)

1 benzene 264 255 220
2 biphenyl 288 248 1,600
3 p-terphenyl 320 276 3,300

4 p-quaterphenyl 340 294 4,000

• as the number of conjugated rings increases, the 0-0 band shifts

to higher wavelengths
• the increase in wavelength is not as fast as the polyenes or
linear aromatics because of the bond between the rings is twisted
• the spectrum is featureless because thermally induced oscillation
about the twist angle adds width to the vibronic bands
• the molar absorptivity increases because the number of double
bonds is increasing
14.2 : 7/8
 Linear Polyphenyls (2)

14.2 : 8/8 R. A. Freidel and M. Orchin, Ultraviolet Spectra of Aromatic Compounds, Wiley, New York, 1951.