Photochemistry of 3,6-Didehydropyridazine Biradical─An Untraceable Para Benzyne Analogue

We report matrix isolation infrared spectroscopic studies to characterize 3,6-didehydropyridazine 6, a heterocyclic analogue of para benzyne, combined with computations. In this regard, we have utilized 3,6-diiodopyridazine 11 as a photolytic precursor. The experiments toward the generation of the biradical are carried out in argon and nitrogen matrices at 4 K. Instead of the elusive biradical, we have observed a ring-opening product maleonitrile ()-7 upon irradiation at 254 nm. In contrast, prolonged irradiation at 254 nm leads only to isomerization, forming fumaronitrile ()-7. The mechanistic aspects of ring-opening, product selectivity, and photoisomerization steps have been investigated in detail using high-level ab initio computations. These studies have found that 3,6-didehydropyridazine 6 is an untraceable intermediate, and the ring-opening step leading to maleonitrile is barrierless. In addition, we have proposed the involvement of the S₁ (π-π*) state via conical intersection in the photoisomerization of maleonitrile.