Long-range magnetic interactions in trans-1,4-cyclohexylene- and 1,3-adamantylene-bis(p-nitrenylbenzene) by pi-sigma-pi hyperconjugation.
[structure: see text]. Di(phenylnitrene)s linked with trans-1,4-cyclohexylene (3) and 1,3-adamantylene (4) units were generated photochemically at cryogenic temperatures. The EPR spectra are attributed to quintets. The temperature dependence of the signal intensities indicates that both quintets are thermally accessible states with energy gaps DeltaE(S-Q) = 138 and 300 J x mol(-1), respectively. DFT calculations showed that the magnetic interactions originated in the pi-sigma-pi hyperconjugative through-bond interactions.
Tukada
H
H
Graduate School of Integrated Science, Yokohama City University, Kanazawa-ku, Yokohama 236-0027, Japan. htht@yokohama-cu.ac.jp
Mochizuki
K
K