Reference

The anodic oxidation of fluorene and some of its derivatives

The anodic oxidation of fluorene and some of its derivatives. Conditions for the formation of a new conducting polymer. Rault-Berthelot, Joelle; Simonet, Jacques (Lab. Electrochim., Univ. Rennes I, Rennes 35042, Fr.). J. Electroanal. Chem. Interfacial Electrochem., 182(1), 187-92 (English) 1985. CODEN: JEIEBC. ISSN: 0022-0728. DOCUMENT TYPE: Journal CA Section: 72 (Electrochemistry) Section cross-reference(s): 35, 76 Fluorene (I) [86-73-7], 9-methylfluorene (II) [2523-37-7],and 9,9'-dimethylfluorene (III) [4569-45-3] were polymd. by electrochem. oxidn. at Pt in a 3-compartment cell with the anode, cathode and ref. electrode being sepd. by a glass frit. Cyclic voltammetry in MeCN for the fluorene polymer for limiting potentials <1.2 V vs. Ag/AgNO3 electrode shows the polymer to be electrochem. stable and not destroyed by charging and discharging. The mode of polymn. does not involve the :CH2 group of I because both II and III lead to the same kind of cyclic voltammetry and analogous polymers. Elemental anal. and the IR spectrum of polyfluorene obtained by const. potential oxidn. of I at 1.35 V in MeCN contg. Bu4NBF4 are in agreement with a salt structure (specific lines BF4- and that of a charge transfer complex 4000 > n > 3000 cm-1). The cond. of the dried sample was very low, although the cond. of the film during growth appeared reasonably large.

Intramolecular Electron Transfer in Cofacially p-Stacked Fluorenes: Evidence of Tunneling

Intramolecular Electron Transfer in Cofacially p-Stacked Fluorenes: Evidence of Tunneling. Rathore, Rajendra; Abdelwahed, Sameh H.; Kiesewetter, Matthew K.; Reiter, Richard C.; Stevenson, Cheryl D. (Department of Chemistry, Illinois State University, Normal, IL 61790-4160, USA). Journal of Physical Chemistry B, 110(4), 1536-1540 (English) 2006 American Chemical Society. CODEN: JPCBFK. ISSN: 1520-6106. DOCUMENT TYPE: Journal CA Section: 22 (Physical Organic Chemistry) (in this abstr. structures F-2 through F-4 represent Me-(fluorenylidene)-CH2-[(fluorenylidene)CH2]n-(fluorenylidene)-Me, n = 0, 1, 2, resp.In this article, certain chemicals are used. One of their cas registry numbers is 4569-45-3 ). The one-electron redn. of neutral p-stacked di- and trifluorenes (F-2 and F-3) in HMPA, where ion assocn. 4569-45-3 is the cas registry number of certain chemical which is used as reagents here. is absent, results in the formation of anion radicals in which the odd electron resides predominantly on just one of the external fluorene moieties, as established by EPR spectroscopy. However, in the case of tetrafluorene, introduction of a single electron leads to a kinetically controlled anion radical F-4(int)·- in which the odd electron undergoes rapid exchange between two central fluorene rings, where the anionic charge is partially shielded from solvation due to the presence of external fluorene rings. On a time scale of minutes, anion radical F-4(int)·- converts to a thermodynamically stabilized anion radical F-4(ext)·-, with the electron exhibiting coupling from the protons on an external fluorene moiety. The charge and spin residing on an external moiety allow efficient solvation of the anionic charge. A similar fast exchange of a single electron (probably with the involvement of quantum mech. tunneling) among three and four internal fluorene moieties is initially obsd. via EPR spectroscopy in the penta- and hexafluorene derivs., F-5 and F-6, resp. ..