Charge transfer complexes between

The structure of the complex of (S)-tryptophan-derived oxazaborolidine 4 and methacrolein has been investigated in detail by use of H, B and NMR [6b. The proximity of the coordinated aldehyde and indole subunit in the complex is suggested by the appearance of a bright orange color at 210 K, caused by formation of a charge-transfer complex between the 7t-donor indole ring and the acceptor aldehyde. The intermediate is thought to be as shown in Fig. 1.2, in which the s-cis conformer is the reactive one. 

Aminopyridines can be perfluoroalkylated in a photoinduced electron transfer process. A charge transfer complex between the heterocycle and polyfluoroalkyl iodide, observable by NMR, is photolytically stimulated... 

Complexes. The structure of an n a charge-transfer complex between quinoxaline and two iodine atoms has been obtained by X-ray analysis and its thermal stability compared with those of related complexes. The hydrogen bond complex between quinoxaline and phenol has been studied by infrared spectroscopy and compared with many similar complexes. Adducts of quinoxaline with uranium salts and with a variety of copper(II) alkano-ates have been prepared, characterized, and studied with respect to IR spectra or magnetic properties, respectively. 

Formation of a Charge Transfer Complex between the nitroxide and one of the oxygen-centered radicals c or d. In the next step the complex is assumed to react with the remaining peroxyradical to form the products actually found, with release of the additive (reactions (13)/(14) or (13 )/(14 )) ... 

The autoinhibiting effect which was apparent in the later stages, particularly for thicker films, was attributed to the formation of charge transfer complexes between HC1 and polyenes. These complexes were assumed to be photochemically inert as far as further dehydrochlorination of the polymer was concerned but may be involved in the reverse process of re-addition of HC1 to the polyenes. The balance between the two effects depends on the ease of diffusion of HC1 out of the film. 

The first example of a donor-acceptor molecular complex was noted in 1949 by Bensei and Hildebrand [137] in their studies involving charge transfer complexes between benzene and molecular iodine. Subsequently such complexes were studied by Mulliken [138] and now more recently have been used by Stoddart et al. [16,139] in designing novel self-assembling systems. 

Charge-transfer complexes between heteroaromatic five-membered ring compounds and tetracyanoethylene have been studied in solution at 20°C.22 Spectra, stability constants, and empirical calculations of ionization energies... 

It is, of course, possible that the charge-transfer complex between metal halide and olefin, which is well known, is an intermediary in this reaction. There is here another variation on the theme of direct initiation. The thermochemical analysis, analogous to the previous ones, goes as follows ... 

Charge transfer complexes between amines and discharged substances were investigated extensively (mainly by spectroscopic methods). The choice of more simple models excludes the presence of proton donor-acceptor interactions which complicate the investigations of other interactions by overlapping different interactions. 

The formation of charge transfer complexes between N,N-dimethylaniline or N,N-diethylaniline and Cspectroscopic studies, also in view of their potential optical and electronic applications. Even if the spectroscopic properties of Cgo, C70 are complicated by the presence of aggregates in room temperature solutions, the emissions from the excited state charge transfer complexes between fullerenes and iVjV-dialkylani lines are strongly solvent-dependent exciplet emissions are observed in hexane, but in toluene they are absent145. 

X-ray structural analysis of the charge-transfer complex between 2,4,7-trinitrofluore-none (80) and 2,6-dimethylnaphthalene shows the presence of C—H- O hydrogen bonding196 involving both nitro and carbonyl groups of 80. These hydrogen bonds importantly influence the molecular arrangement in a nearly coplanar ribbon-like structure also for other aromatic and aliphatic nitro derivatives. 

The feasible formation of charge-transfer complexes between various organic compounds (e.g., pesticides and herbicides), PAHs and polychlorinated bi-... 

This means that 4-nitrostilbene is a more effective electron acceptor than nitrobenzene. This theoretical conclusion is verified by experiments. The charge-transfer complexes formed by nitrobenzene or 4-nitrostilbene with Af,Af-dimethylaniline have stability constants of 0.085 L mol or 0.296 L mol respectively. Moreover, the formation of the charge-transfer complex between cis-4-nitrostilbene and A/,Af-dimethylaniline indeed results in cis-to-trans conversion (Dyusengaliev et al. 1995). This conversion proceeds slowly in the charge-transfer complex, but runs rapidly after one-electron transfer leading to the nitrostilbene anion-radical (Todres 1992). The cis trans conversion of ion-radicals will be considered in detail later, (see sections 3.2.5.1, 6.4, and 8.2.1). 

Fig. 7. Stacking of molecules in crystals of a charge-transfer complex between thianthrene and the dimer of quinone.

Rauhut and coworkers proposed the occurrence of a charge transfer complex between the HEI and the ACT in order to explain the electronically excited-state generation in the peroxyoxalate system. Chemiluminescence quantum yield (4>cl) measurements with different activators have shown that the lower the ACT half-wave oxidation potential (Ei/2° ) or singlet energy (Es), the higher the electronically excited-state formation rate and 4>cl- According to the mechanistic proposal of Schuster and coworkers for the CIEEL... 

Evaluation of the UV-visible spectra has been used to demonstrate the formation of charge transfer complexes between the acridizinium (benzo[6]quinolizinium) ion and polycyclic aromatic hydrocarbons (78ZC33). Similar measurements have been employed to demonstrate the existence of an interaction between DNA and coralyne, a dibenzo[a,g]-quinolizinium salt (76JMC1261). 

In addition to ferrocene, the oxidative redox couple that has received the most attention in supramolecular chemistry is tetrathiofulvalene (TTF), 35. This compound undergoes two reversible one-electron oxidations, first to a radical cation and then to a dication (Eq. 1.21). TTF first came to prominence in the 1970s when it was discovered that the charge transfer complex between it and 7,7,8,8-tetracyanoquinonedimethane (TCNQ) shows metallic conductivity. As a result, a large variety of different TTF derivatives have been prepared and characterized. This rich synthetic chemistry, coupled with the electroactivity, has intrigued supramolecular chemists for some time, with the result that the TTF unit has been incorporated into a wide variety of... 

When two polymeric systems are mixed together in a solvent and are spin-coated onto a substrate, phase separation sometimes occurs, as described for the application of poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor for a Novolak resin (4). There are two ways to improve the compatibility of polymer mixtures in addition to using a proper solvent modification of one or both components. The miscibility of poly(olefin sulfones) with Novolak resins is reported to be marginal. To improve miscibility, Fahrenholtz and Kwei prepared several alkyl-substituted phenol-formaldehyde Novolak resins (including 2-n-propylphenol, 2-r-butylphenol, 2-sec-butylphenol, and 2-phenylphenol). They discussed the compatibility in terms of increased specific interactions such as formation of hydrogen bonds between unlike polymers and decreased specific interactions by a bulky substituent, and also in terms of "polarity matches" (18). In these studies, 2-ethoxyethyl acetate was used as a solvent (4,18). Formation of charge transfer complexes between the Novolak resins and the poly (olefin sulfones) is also reported (6). 

Radical iodination of simple alkenes was found to take place more readily than the ionic process. The addition is anfi-stereoselective,250,251 resulting from an attack of iodine atom or molecule on charge-transfer complex between the alkene and an iodine molecule or atom. 

Charge transfer complexes between various phenanthrolines and tetracyano-p-quinodimethane have been patented as inks and copying materials because of their high color.300... 

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