Why homoannular diene in uv spectrometry have higher wavlenth than hetroannular diene?

Homoanular dienes have a greater base value than heteroanular dienes

Explanation:

Woodward in 1945 gave a set of rules relating the wavelength of maximum absorption to the structure of a compound. These rules were modified by Fieser in 1959. These sets of rules describe the absorption of organic molecules in the UV region of the electromagnetic spectrum.

Each system of diene or triene has a given fixed value at which maximum absorption is expected to occur according to Woodward rules. This given fixed value is called the base or parent value. If the two double bonds are trans to each other, the diene is said to be transoid. If the two double bonds belong to different rings, the system is said to be heteroanular and the base value in each case is 215nm. If the double bonds are cis to each other (cisoid), or the two double bonds are in the same ring (homoanular), then the base value is 253nm.

Since λmax = base value + ∑ substituent contributions + ∑ other contributions, if the other contributions are not very significant, homoanular diene will have a greater λmax because of its larger base value compared to heteroanular diene. This correlates well with the fact that conjugated systems absorb at a longer wavelength.

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