M-phenylene-linked aromatic poly(aminium cationic radical)s: Persistent high-spin organic polyradicals

Organic Letters

Volumn 5, Issue 12, 2003, Pages 2165-2168

  Michinobu, Tsuyoshi ^a   Inui, Jun ^a   Nishide, Hiroyuki ^a  

^a WASEDA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC AMINE; FERROMAGNETIC MATERIAL; PALLADIUM; PHENYL GROUP; POLYAMINE DERIVATIVE; RADICAL;

ARTICLE; CATALYSIS; CATALYST; MOLECULAR INTERACTION; MOLECULAR WEIGHT; OXIDATION; POLYMERIZATION;

EID: 0141630560     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0346281     Document Type: Article

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35. 2 often resulted in the production of a dark gel with a short half-life (e.g., 3 h for the polyradical of poly-1) even if <1.0 equiv of the oxidant was added. The position protonated by TFA seems to be overlapped with the spin density distribution of the aminium cationic radical, which prevents the intra- or intermolecular dimerization of the radicals.
36. s plots tend to decrease at high fields due to low S fractions.
37. Atomic force microscopy measurement of poly-1 on mica at room temperature clearly revealed that an average vertical distance of the single polymer (about 500 samples) decreased from 1.43 to 0.83 nm after the chemical oxidation, indicating the higher π-coplanarity for the polyradical.
38. 6 in the presence of 9 vol % of TFA reasonably decreased to 3/2 with a spin concentration of 0.38. The addition of TFA is essential for the present results and discussion, because the polyradical with a low spin concentration oxidized in the absence of TFA only displayed S = 1/2 - 2/2, consistent with the electrochemical measurements. However, the possibility of the magnetic impurities in TFA was ruled out from the magnetic measurement of the background media including TFA.