Direct Detection of Singlet Cyclopentane-1,3-diyl Diradicals By Infrared and Ultraviolet-Visible Spectroscopy at Cryogenic Temperature and Their Photoreactivity.

Abstract

Photolysis of a 7,7-difluoro-1,4-diphenyl-2,3-diazabicyclo[2.2.1]hept-2-ene derivative (AZ1) using a 365 nm light-emitting diode in an Ar matrix at 4 K resulted in the formation of a planar singlet 2,2-difluoro-1,3-diphenylcyclopentane-1,3-diyl diradical derivative, S-DR1-pl (λmax = 520 nm). A singlet cyclopentane-1,3-diyl diradical system (S-DR1-pl) was directly detected by steady-state infrared (IR) spectroscopy. Due to the photolability of S-DR1-pl, initial photolysis of AZ1 also yielded the ring-closed product ret-CP1 and migration products trans-MG1 and/or cis-MG1, which were observed using IR spectra. Monitoring of prolonged photolysis using IR and ultraviolet-visible (UV-vis) spectra demonstrated the formation of the allylic cation CT1 (λmax = 470 nm). On the other hand, photolysis of a 7,7-dimethoxy-1,4-diphenyl-2,3-diazabicyclo[2.2.1]hept-2-ene derivative (AZ2) yielded a puckered conformer (instead of planar) of the corresponding diradical S-DR2-puc, which was detected by IR and UV-vis spectroscopy in an Ar matrix at 4 K. This spectroscopic characterization opens a new strategy to obtain more detailed information about the structure and reactivity of singlet cyclopentane-1,3-diyl diradicals.