Intercage electron transfer driven by electric field in Robin-Day-type molecules.
A new class of isomers, namely, intercage electron-transfer isomers, is reported for fluorinated double-cage molecular anion e(-)@C(20)F(18)(NH)(2)C(20)F(18) with C(20)F(18) cages: 1 with the excess electron inside the left cage, 2 with the excess electron inside both cages, and 3 with the excess electron inside the right cage. Interestingly, the C(20)F(18) cages may be considered as two redox sites existing in a rare nonmetal mixed-valent (0 and -1) molecular anion. The three isomers with two redox sites may be the founding members of a new class of mixed-valent compounds, namely, nonmetal Robin-Day Class II with localized redox centers for 1 and 3, and Class III with delocalized redox centers for 2. Two intercage electron-transfers pathways involving transfer of one or half an excess electron from one cage to the other are found: 1) Manipulating the external electric field (-0.001 a.u. for 1→3 and -0.0005 a.u. for 1→2) and 2) Exciting the transition from ground to first excited state and subsequent radiationless transition from the excited state to another ground state for 1 and 3. For the exhibited microscopic electron-transfer process 1→3, 2 may be the transition state, and the electron-transfer barrier of 6.021 kcal mol(-1) is close to the electric field work of 8.04 kcal mol(-1).
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, China.
Yin-Feng
YF
Wang
Ying
Y
Li
Zhong-Jun
ZJ
Zhou
Zhi-Ru
ZR
Li
Di
D
Wu
Jiangen
J
Huang
Feng Long
FL
Gu