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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 max (nm) max (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 max (nm) max (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) 0-0 (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) max(nm) max (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.