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My teacher has told us that ClO2 does not dimerise due to delocalization of unpaired electron, but didn't elaborate on this. I didn't understand it.

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    $\begingroup$ The same question could be asked about the molecule NO. The reason may be that dimerization would produce a non-bonding molecular orbital. So Nature is reluctant to produce non-bonding orbitals. $\endgroup$
    – Maurice
    Aug 9, 2023 at 12:26
  • $\begingroup$ The unpaired electron goes in a non-bonding orbital - as above. In the single molecule this weakens the bond - i.e. the 3 electron bond is weaker than the C=O bond. As mentioned above - as it's non-bonding - and therefore higher energy - presumably the dimer would be rather unstable. $\endgroup$ Aug 9, 2023 at 12:39
  • $\begingroup$ All radicals dimerise, or even polymerise, to some extent, at least in low temperature. The resulting bonds may be so weak the equilibrium of thermal decomposition is far to the right at room temp., though. $\endgroup$
    – Mithoron
    Aug 9, 2023 at 13:31
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    $\begingroup$ @Maurice $\ce{NO}$ foes dimerize when condensed, and this plays some roke in its relatively high boilimg point for a diamotic molecule. $\endgroup$ Aug 9, 2023 at 13:46
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    $\begingroup$ @Oscar Lanzi. Yes. NO dimerizes at rather low temperatures, well under $0$°C. I was speaking of the chemistry at usual temperatures, above $0$°C. I agree I should have mentioned it previously. $\endgroup$
    – Maurice
    Aug 9, 2023 at 14:28

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