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Optically and Thermally Induced Electron Transfer Pathways in Hexakis[4‐( N,N ‐diarylamino)phenyl]benzene Derivatives
Author(s) -
Lambert Christoph,
Nöll Gilbert
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020802)8:15<3467::aid-chem3467>3.0.co;2-1
Subject(s) - electron transfer , redox , chemistry , photochemistry , electrochemistry , electron , ground state , benzene , chemical physics , potential energy surface , molecule , atomic physics , electrode , inorganic chemistry , organic chemistry , physics , quantum mechanics
The optically and thermally induced electron transfer pathways of highly symmetrical ( D 3 ) hexaarylbenzene systems with six triarylamine redox sites have been investigated. Owing to slightly different local redox potentials, the radical trication could be selectively generated by electrochemical methods. This trication shows a strong intervalence charge‐transfer band in the near infrared (NIR) that was measured by spectroelectrochemistry and analysed using multi‐dimensional Mulliken–Hush theory. Quantum chemical AM1 CI calculations indicate that there is no optically induced concerted three‐electron transfer that transforms the ground state into a state in which all three positively charged triarylamine moieties change place with their neutral neighbours. The potential energy surface of the ground state was constructed by using quadratic potentials. From this potential surface it is apparent that there is also no thermally allowed concerted three‐electron transfer pathway. Instead, three consecutive one‐electron transfer steps are necessary for this process.