Parity and heteroatom effects on open-shell exchange interactions: nitrenophenyl iminoylnitroxides.
Photolysis of pN3PhIN and mN3PhIN in frozen matrix yields pNPhIN and mNPhIN, respectively. pNPhIN gives a quartet state with nonlinear ESR intensity behavior (|D/hc| = 0.300 cm(-1), |E/hc| congruent with 0.0 cm(-1)); mNPhIN gives a thermally excited quartet state (|D/hc| = 0.336 cm(-1), |E/hc| = 0.006 cm(-1)) with inverse Curie behavior. Computations show little nitrene delocalization onto the radicals even for the para system. The NPhIN systems behave differently from analogous nitronylnitroxides due to asymmetric radical spin distribution. [reaction: see text]
Taylor
Patrick
P
Department of Chemistry, University of Massachusetts, Amherst, MA 01003, USA.
Serwinski
Paul R
PR
Lahti
Paul M
PM