Electron donor-acceptor compounds application

In this chapter, we will discuss the recent results regarding the development of molecular switches and logic gates toward information processing at the molecular level based on electroactive molecules and supramolecules. Also, we will illustrate the progress of application of electron donor-acceptor compounds in high-density information storage. 

Non-fused iron catalysts have been studied earlier. The famous Uhde catalyst was KAl (Fe(CN)6), which was used, to be applied in industry. It was abandoned because of its poor stability, and up to now there are still reports about its modifications. Intermetallic compound and alloy catalysts, such as LaNij, FeTi, Fe2Ce and FeZr etc., were also expected to be prospective, but until now they have not been put into practice. In 1970s, the well-known electron donor-acceptor (EDA) catalysts, e.g., phthalocyanine iron-alkali metal, molysite — graphite — potassium and ferrocene-activated carbon-potassium catalyst systems, were found to have the ability to synthesize ammonia under mild conditions in the laboratory. Unfortunately, their activities declined rapidly in the experiments of scale-up. The application of EDA catalysts in industry turned to be a visionary. Therefore, replacement of fused iron catalyst is not an easy thing for a very long time. 

The eleven examples of TABLE 4 based on electron-donor compounds of family 3b show that induction processes starting from either non-mesomorphic or nematic discotic precursors can indeed give the ( intermediate kind of) stable colunmar nematic phase including the three known cases of chiral nematic phases. Unfortunately, for application purposes the temperature ranges of the nematic phases of the intermolecular electron donor-acceptor complexes (TABLE 4) may be much too high ... 

Much earlier information on the structure of diazonium ions than that derived from X-ray analyses (but still useful today) was obtained by infrared spectroscopy. The pioneers in the application of this technique to diazonium and diazo compounds were Le Fevre and his school, who provided the first IR evidence for the triple bonds by identifying the characteristic stretching vibration band at 2260 cm-1 (Aroney et al., 1955 see also Whetsel et al., 1956). Its frequency lies between the Raman frequency of dinitrogen (2330 cm-1, Schrotter, 1970) and the stretching vibration frequency of the C = N group in benzonitrile (2255 cm-1, Aroney et al., 1955). In substituted benzenediazonium salts the frequency of the NN stretching vibration follows Hammett op relationships. Electron donor substituents reduce the frequency, whereas acceptor substituents increase it. The 4-dimethylamino group, for example, shifts it by 103 cm-1 to 2177 cm-1 (Nuttall et al., 1961). This result supports the hypothesis that... 

For instance, Kochi and co-workers [89,90] reported the photochemical coupling of various stilbenes and chloranil by specific charge-transfer activation of the precursor donor-acceptor complex (EDA) to form rrans-oxetanes selectively. The primary reaction intermediate is the singlet radical ion pair as revealed by time-resolved spectroscopy and thus establishing the electron-transfer pathway for this typical Paterno-Biichi reaction. This radical ion pair either collapses to a 1,4-biradical species or yields the original EDA complex after back-electron transfer. Because the alternative cycloaddition via specific activation of the carbonyl compound yields the same oxetane regioisomers in identical molar ratios, it can be concluded that a common electron-transfer mechanism is applicable (Scheme 53) [89,90]. 

Mechanically interlocked molecular compounds, including catenanes, rotax-anes, and carceplex, are constituted of molecules composed of two or more components that cannot be separated from each other [95-98]. The development of strategy for achieving controlled self-assembling systems by non-covalent interaction enables one to prepare such attractive compounds for applications in nanoscale molecular devices. The dithiafulvene derivatives are effective electron donors, which are good candidates to form those supramolecular systems with appropriate acceptors by virtue of intermolec-ular CT interactions. In this chapter, dithiafulvene polymers forming rotax-ane structures are especially described. 

Recent work has investigated the potential to control the partitioning of charge in branched arrays [230]. This has many potential applications to the development of photoactive networks and dendritic systems capable of electron transfer. Compounds 17 and 18 employ 1,3,5-triaminobenzene as the central branch point. In each molecule ANI is attached to the 1 position and serves as the electron donor. The electron acceptors again are NI and PI, and are attached to the 3 and 5 positions, respectively in compound 17. Excitation of ANI with 400 nm laser pulses results in electron transfer exclusively to the NI branch. This is due to the 0.3 V... 

Metal ions can act as electron-pair acceptors, reacting with electron donors to form coordination compounds or complex ions. The donor species, or ligand, must have at least one pair of unshared electrons to form the bond. Remarkable growth in the analytical applications of complex-formation reactions is attributable to a particular class of coordination compounds called chelates. These compounds are made by the reaction of a metal ion and a ligand that contains two or more donor groups. The properties of chelates can differ markedly from the parent cation. 

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