Fluorene cation

Loss of ethylene and subsequent formation of the stable 3//-pyrrolinine cation dominates the mass spectrum of 2,3,4,5-tetrahydro-l//-l-benzazepine <75OMS(10)992). Biphenylene (m/e 152), acridinium cation (m/e 179) and fluorene cation (m/e 165) are the major fragments in the mass spectra of dibenz[T>,/]azepines (74CJRV101). 

The nature of the DNA adduct remains to be determined. However the spectrum of the isolated DNA is similar to that of the DNA adduct formed when 2-aminodifluorenylamine is oxidized by a peroxidase-H202 reaction mixture. Furthermore a similar DNA adduct is formed when DNA is added at a time when the blue imino derivative is maximal. Furthermore in the presence of DNA much less extractable azofluorene, aminodif luoreny lamine or polymer was formed suggesting that DNA reacts with the amino-fluorene cation radical and 2-iminodifluorenylamine. 

Oxidation of some fluorene derivatives, such as 1-hydrofluorene or fluorene-1-carboxylic acid, does not produce polymer films. Two explanations have been proposed [186]. First, strong electron withdrawing groups such as carboxylic acid may destablize the fluorene radical cation and promote reactions with the solvent or anions. Conversely, donor substituents such as hydroxyl groups may stabilize the fluorene cation radical intermediates enough so that the radicals may diffuse away... 

The complexes precipitate immediately on mixing 1 1 complexes (n = 1) are prepared from arenes such as benzene, biphenyl, naphthalene, acenaphthalene, fluorene, phenanthrene, anthracene and m-dinitrobenzene. These complexes contain a complex Hg(I) cation with the arene v coordinated to one Hg as in III ... 

Li, Na, or Grignard compounds of cyclopentadiene, indene, or fluorene add to di-substituted cyclopropenium cations forming cyclopentadienyl cyclopropenes, which can be transformed to calicenes by subsequent hydride abstraction and deprotonation, as shown by the following examples 9S91 and 9992 (cf. p. 13) ... 

The electrogenerated radical anions of aromatic hydrocarbons, e.g. DPA, rubrene, fluorene, can also act as reductants towards electro-chemically obtained radical cations which are derivatives of other aromatic compounds such as N,N-dimethyl-/>-phenylenediamine (Wurster s red) 150> (see Section VIII. B.). When a mixture of DPA and a halide such as 99 (DPACI2) or 100 is electrolysed, a bright chemiluminescence is observed the quantum yields are about two orders of magnitude higher than that of the DPA radical anion-radical cation reaction 153>. 

Pei and coworkers [362] synthesized fluorene copolymer functionalized with imidazole ligands in the side chains (270). The PL emission of 270 was sensitive to the presence of metal cations in solution (particularly efficient quenching was due to Cu2+), which makes it a promising material for fluorescent chemosensing. 

Fluorene-[2,5-di(aminoethoxy)benzene] copolymers 370a,b have been synthesized by Huang and coworkers [437,438] as precursors to the first water-soluble cationic PFs 371, 372a-c (Scheme 2.58). Whereas the neutral polymers 370a,b readily dissolve in common organic solvents such as THF, chloroform, toluene, and xylene (but not in dimethyl sulfoxide (DMSO), methanol, or water) their quaternization produces material 371, which is insoluble in chloroform or THF but completely soluble in DMSO, methanol, and water. For... 

We then focused our attention to the cationic species generated from a series of condensed aromatics fully annelated with BCO units. Newly synthesized naphthalene 12 (17), anthracene 13 (18), biphenylene 14 (19), and fluorene 15 (20) all underwent smooth one-electron oxidation by the use of 1.5... 

We have not yet prepared the unsubstituted indenylidene fluorene dication 17 but the NICSO) (18) values demonstrate that the fluorenyl cation is still more antiaromatic than the indenyl cation, see Table III. 

The antiaromaticity of indenyl cations was examined in the dications of indenylidene fluorenes. Contrary to expectation, the fluorenyl cation was more antiaromatic than the indenyl cation in these systems. The sum of NICS(l)zz values was linearly related to global measures of antiaromaticity such as A, suggesting that they could be used to evaluate antiaromaticity in a local sense, for individual rings. 

Intensive effort has been devoted to the optimization of CCP structures for improved fluorescence output of CCP-based FRET assays. The inherent optoelectronic properties of CCPs make PET one of the most detrimental processes for FRET. Before considering the parameters in the Forster equation, it is of primary concern to reduce the probability of PET. As the competition between FRET and PET is mainly determined by the energy level alignment between donor and acceptor, it can be minimized by careful choice of CCP and C. A series of cationic poly(fluorene-co-phenylene) (PFP) derivatives (IBr, 9, 10 and 11, chemical structures in Scheme 8) was synthesized to fine-tune the donor/acceptor energy levels for improved FRET [70]. FI or Tex Red (TR) labeled ssDNAg (5 -ATC TTG ACT ATG TGG GTG CT-3 ) were chosen as the energy acceptor. The emission spectra of IBr, 9, 10 and 11 are similar in shape with emission maxima at 415, 410, 414 and 410 nm, respectively. The overlap between the emission of these polymers and the absorption of FI or TR is thus similar. Their electrochemical properties were determined by cyclic voltammetry experiments. The calculated HOMO and LUMO... 

Liu B, Dan TTT, Bazan GC (2007) Collective response from a cationic tetrahedral fluorene for label-free DNA detection. Adv Funct Mater 17 2432-2438... 

One case of n—5 —n delocalization was demonstrated by Stevenson et al. (2006). The potassinm anion-radical salt of l-(9-methyl-9H-fluoren-9-yl)-4-methyl benzyl is characterized by the delocalization of an nnpaired electron within the fluorenyl moiety only. Its ESR spectrnm completely coincides with the spectrnm of the potassium anion-radical salt of the 9,9-dimethyl fluorene anion-radical in THE However, the cesium anion-radical salt of the fluorenyl methylbenzyl derivative produces the ESR spectrum corresponding to the placement of this cation between the fluorenyl and methylbenzyl moiety. The conditions of n—s—n delocalization appear An unpaired electron spends its time within both fluorenyl and methylbenzyl fragments. The situation is explained in Scheme 3.54. 

The jS-trimethylsilyl group in 212 weakens the C—H bond by 16 kcalmol-1 compared with the C—H bond in fluorene 207. Comparing the data for the tertiary C—H bonds from Table 6, the /i-H-substituted fluorenyl cation (from 208) is less stable by 8 kcalmol-1, and... 

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