Electronic Spectroscopy or UV-Visible spectroscopy

Woodward-Fieser rule for predicting the lmax Polyenes

• Summarized by R.B. Woodward, L.F. Fieser and others

• Predict lmax for π → * in extended conjugation systems

References : 1. Spectroscopy by Lampman, Pavia, Kriz, Vyvyan

Woodward-Fieser rule for predicting the lmax Polyenes

Heteroannular & Homoannular

➢ Repulsion between terminal lobes of Ψ2 increases energy of HOMO in s-cis form.

➢ Hence, less energy (ie. Higher wavelength) is required for Ψ2 → Ψ3* transition.

➢ Substitution may force a molecule to take s-cis form,

➢ Absorbs energy from a longer wavelength (shows a
red shift) than usual s-trans conformer.
 Woodward-Fieser rule for predicting the lmax Polyenes

Some Worked Examples

Base value 214
Acyclic, 2 x alkyl subst. 10
Heteroannular, Homoannular, exo DB 5
Base 214 nm
Base 214 nm Base 253 nm total 229
==================
Attached group Increment, (nm) Obs. 227

Extend conjugation +30 Base value 214

Addn exocyclic DB +5 3 x alkyl subst. 15
exo DB 5
Substituent effect total 234
Alkyl +5 Obs. 235

O-Acyl 0
S-alkyl +30 Base value 253
4 x alkyl subst. 20
O-alkyl +6 2 x exo DB 10
NR2 +60 total 283
Obs. 285
Cl, Br +5
Woodward–Fieser Rules for Diene
Woodward–Fieser Rules for Diene

Base value 214

Base value 214 5 x alkyl subst. 25
6 x alkyl subst. 30 4 x Ext. Conjugation 120
5 x Ext. Conjugation 150 2 x exo DB 10
2 x exo DB 10 OR substitution 6
NR2 substitution 60 Halogen 5
Total 464 Total 380