A Redox‐Active Microporous Organosiloxane Containing a Stable Neutral Radical, Trioxotriangulene

• Published in: Chemistry : a European journal Vol. 28; no. 12; pp. e202104447 - n/a
• Main Authors: Murata, Tsuyoshi, Asakura, Noriaki, Tsuji, Ryotaro, Kanzaki, Yuki, Sato, Kazunobu, Takui, Takeji, Morita, Yasushi
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 24.02.2022
• Subjects: Chemistry; Diamagnetism; Diameters; Dimers; Electrochemistry; multistage redox ability; organic rechargeable battery; Oxidants; Oxidizing agents; polycyclic aromatic molecule; porous organosiloxane; Reducing agents; stable neutral radical; polycyclic aromatic molecule; organic rechargeable battery; multistage redox ability; stable neutral radical; porous organosiloxane
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202104447

A new silyl‐substituted trioxotriangulene (TOT) neutral radical and corresponding porous organosiloxanes (POSs) were synthesized. The neutral radical exhibited a peculiarly high stability and formed a diamagnetic π‐dimer characteristic to TOT neutral radicals stabilized by the strong multiple SOMO‐SOMO interaction in both solution and solid states. POSs including TOT units within the organosiloxane‐wall were prepared by polycondensation of the silyl groups and formed microporous structures with ∼1 nm‐size diameters. Redox ability of TOT units in the POS was demonstrated by the treatment of oxidant/reductant in heterogeneous suspension condition, where the TOT units were reversibly converted between reduced and neutral radical species. Furthermore, the solid‐state electrochemical measurements of the POS revealed the reversible multi‐stage redox ability of TOT units involving polyanionic species within the organosiloxane‐wall. A new silyl‐substituted trioxotriangulene (TOT) neutral radical was synthesized and exhibited a peculiarly high stability and a self‐assembling ability to form a π‐dimer stabilized by the strong multiple SOMO‐SOMO interaction. The polycondensation of the silyl‐substituted TOT yielded a microporous organosiloxane with a large surface area and a micropore of ∼1 nm diameter. The TOT unit incorporated in the organosiloxane‐wall exhibited a reversible multi‐stage redox ability in the chemical and electrochemical methods.