Electron donor—acceptor interactions

In a similar fashion the bonding in H2 might be formally regarded as a complementary pair of one-electron donor-acceptor interactions, one in the ot (spin up ) and the other in the 3 (spin down ) spin set.8 In the long-range diradical or spin-polarized portion of the potential-energy curve, the electrons of ot and (3 spin are localized on opposite atoms (say, at on HA and 3 on HB), in accordance with the asymptotic dissociation into neutral atoms. However as R diminishes, the ot electron begins to delocalize into the vacant lsB(a) spin-orbital on HB, while (3 simultaneously delocalizes into Isa on HA, until the ot and (3 occupancies on each atom become equalized near R = 1.4 A, as shown in Fig. 3.3. These one-electron delocalizations are formally very similar to the two-electron ( dative ) delocalizations discussed in Chapter 2, and they culminate as before (cf. Fig. 2.9) in an ionic-covalent transition to a completely delocalized two-center spin distribution at... 

It has not yet been clarified whether the ring substituents interact directly with the binding site or affect the molecular characteristics of the DHP molecules in common. A recently used atomistic pseudoreceptor model for a series of DHP indicated a putative charge-transfer interaction was stabilizing the DHP-binding site complex [19]. To prove this hypothesis qualitative and quantitative analysis of the molecular orbitals of nine DHP derivatives (Fig. 9.11) was performed [18]. Charge-transfer (or electron-donor-acceptor) interactions are indicative of electronic... 

In host-guest systems based on electron donor/ acceptor interactions, association/dissociation can be driven by redox processes so that it is possible to design electrochemical switches than can be used to control energy- and electron-transfer processes. 

Interactions between aliphatic amines (n-donors) and benzonitrile139 or dicyanoben-zenes140,141 (jr-acceptors), in n-hexane, are mainly electron donor-acceptor interactions. It is reasonable to assume that the lone-pair of the donor is perpendicular to the plane of the acceptor as reported in 42 for 1,4-dicyanobenzene. 

Electron Donor-Acceptor Interaction (Charge Transfer). 135... 

This is a case of electron donor-acceptor interaction, the electron donor being the basic component. It may therefore be expected that for a given electron acceptor gradations of donor strength should be recognizable as gradations of basicity. 

There are a number of different enthalpic interactions that can occur between polymer and packing, and in many cases multiple interactions can exist depending on the chemical structure of the polymer. Enthalpic interactions that are related to water-soluble polymers include ion exchange, ion inclusion, ion exclusion, hydrophobic interactions, and hydrogen bonding (12)- Other types of interactions commonly encountered in SEC, as well as in all other chromatographic separations, are dispersion (London) forces, dipole interactions (Keeson and Debye forces), and electron-donor-acceptor interactions (20). 

In the absence of electron donor-acceptor interactions, the London dispersive energy is the dominant contributor to the overall attractions of many molecules to their surroundings. Hence, understanding this type of intermolecular interaction and its dependency on chemical structure allows us to establish a baseline for chemical attractions. If molecules exhibit stronger attractions than expected from these interactions, then this implies the importance of other intermolecular forces. To see the superposition of these additional interactions and their effect on various partitioning phenomena below, we have to examine the role of dispersive forces in more detail,... 

Surface Adsorption Due to Electron Donor-Acceptor Interactions... 

Figure 11.1. Schematic views of various ways in which an organic chemical, i, may sorb to natural inorganic solids (a) adsorption from air to surfaces with limited water presence, (b) partitioning from aqueous solutions to the layer of vicinal water adjacent to surfaces that serves as an absorbent liquid, (c) adsorption from aqueous solution to specific surface sites due to electron donor-acceptor interactions, (d) adsorption of charged molecules from aqueous solution to complementarily charged surfaces due to electrostatic attractions, and (e) chemisorption due to surface bonding or inner sphere complex formation.

Table 11.2 Adsorption of Nonionic Nitroaromatic Compounds (NACs) to Aluminosilicate Clays (a) Surface Area Factors,/saf, for Different Clays Expressing Maximum Sorption Sites Relative to Kaolinite, and (b) KNAC EDA Values (L- mol 1 sites) Measured for Several NACs on K+-Kaolinite Allowing Estimates of KNACd Values Due to Electron Donor-Acceptor Interactions (Eq. 11-20) ...

Our calculations predict only minor differences between the ground state dipole moments for molecules containing nitro electron acceptors versus those possessing methylsulfonyl. In contrast, the hyperpolarizabilities behave much differently, in that calculated J3Z for the aminonitrostilbenes is about twice that of the aminosulfonylstilbenes and the nitroanilines are more than 5 times more nonlinear than the sulfonylanilines. The hyperpolarizabilities appear to be very sensitive to the details of the electron donors-acceptor interaction and hence accentuate the differences in the a values for nitro and methylsulfonyl. 

Lately one has been able to encounter experimental studies more frequently denoted Chemical Force Microscopy , CMF. This includes various attempts to observe tip-surface interactions which are specific to the chemical constitution of the surface. Mostly, CFM involves modification of the tip by a surface layer with molecules which contain particular functional groups, i.e. hydrophilic or hydro-phobic moieties, hydrogen bonding groups, ionic substituents and molecular units which can undergo electron-donor-acceptor interactions. However, sometimes the term Chemical Force Microscopy is just used for any method which can provide a material specific contrast. Depending on the specificity, CFM provides valuable information on the nanoscale composition complementary to other surface characterisation methods which are sensitive to the chemical con-... 

Ferguson, S. B., Sanford, E. M., Seward, E. M., Diederich, F., Cyclophane arene inclusion complexation in protic solvents - solvent effects versus electron-donor acceptor interactions. J. Am. Chem. Soc. 1991, 113, 5410-5419. 

Renata Marczak, Mateusz Wielopolski, S. Shankara Gayathri, Dirk M. Guldi, Yutaka Matsuo, Keiko Matsuo, Kazukuni Tahara, Eiichi Nakamura. Uniquely Shaped Double-Decker Buckyferrocenes-Distinct Electron Donor-Acceptor Interactions. J. Am. Chem. Soc. 2008, 130, 16207. 

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