TY - JOUR
T1 - Stable Spiro-Fused Diarylaminyl Radicals
T2 - A New Type of a Neutral Mixed-Valence System
AU - Sentyurin, Vyacheslav V.
AU - Levitskiy, Oleg A.
AU - Bogdanov, Alexey V.
AU - Yankova, Tatiana S.
AU - Dorofeev, Sergey G.
AU - Lyssenko, Konstantin A.
AU - Gontcharenko, Victoria E.
AU - Magdesieva, Tatiana V.
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2023/8/1
Y1 - 2023/8/1
N2 - A new type of neutral mixed-valence system was synthesized using a facile one-pot procedure. The spiro-conjugated framework is additionally “fastened” with a biphenyl bridge, which does not directly participate in spin delocalization but makes the molecule stable and influences the reorganization energy and the energy barrier of the intramolecular electron transfer. The in-depth experimental and quantum-chemical study allowed determining the radicals as the Class II Robin-Day-mixed-valence systems. The structure of the radicals was confirmed by the X-ray data, which are relatively rare for Class II MV molecules. Advanced properties of the radicals, such as an ambipolar redox behavior and panchromatic absorption in the visible and NIR regions, along with their stability, make them of interest for materials science. All radicals demonstrate the SOMO-HOMO inversion phenomenon, which was supported by the DFT and the experimental study.
AB - A new type of neutral mixed-valence system was synthesized using a facile one-pot procedure. The spiro-conjugated framework is additionally “fastened” with a biphenyl bridge, which does not directly participate in spin delocalization but makes the molecule stable and influences the reorganization energy and the energy barrier of the intramolecular electron transfer. The in-depth experimental and quantum-chemical study allowed determining the radicals as the Class II Robin-Day-mixed-valence systems. The structure of the radicals was confirmed by the X-ray data, which are relatively rare for Class II MV molecules. Advanced properties of the radicals, such as an ambipolar redox behavior and panchromatic absorption in the visible and NIR regions, along with their stability, make them of interest for materials science. All radicals demonstrate the SOMO-HOMO inversion phenomenon, which was supported by the DFT and the experimental study.
UR - http://www.scopus.com/inward/record.url?scp=85162711837&partnerID=8YFLogxK
U2 - 10.1002/chem.202301250
DO - 10.1002/chem.202301250
M3 - Article
AN - SCOPUS:85162711837
SN - 0947-6539
VL - 29
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 43
M1 - e202301250
ER -