ABSTRACT
Photolysis of 1a yields 4a in argon-saturated methanol, whereas 1b is photostable. Laser flash photolysis of 1a in acetonitrile shows formation of biradical 2a (lambda(max) = 340 nm, tau = approximately 60 ns), which undergoes intersystem crossing to form Z-3a (lambda(max) = 380 nm, tau = 270 ns) and E-3a (lambda(max) = 380 nm, tau = 300 ms). Z-3a regenerates the starting material, whereas E-3b undergoes intramolecular lactonization to release the alcohol moiety and form 4a. Similar laser flash photolysis of 1b shows formation of biradical 2b (lambda(max) = 340 nm, tau = 1.9 micros in acetonitrile), which is longer-lived than 2a is. However, 2b only undergoes intersystem crossing to form Z-3b (lambda(max) = 380 nm, tau = 4.3 micros). Calculations demonstrate that intramolecular pseudo hydrogen bonding between the OH moiety and the radical centered on the isopropyl carbon in 2b and the bulkiness of the isopropyl group prevent the necessary rotation to form E-3b. In comparison, 2a does not form an intramolecular pseudo hydrogen bond between the methylene radical center and the OH group, and as a consequence, it undergoes intersystem crossing to form both E- and Z-3a.
