Charge-transfer character

Recently the solvent effect on the [4+2] cycloaddition of singlet oxygen to cyclic dienes has been subjected to a multiparameter analysis. A pre-equilibrium with charge-transfer character is involved, which is affected by the solvent through dipolarity-polarisability (n ) and solvophobic interactions ( Sjf and Another multiparameter analysis has been published by Gajewski, demonstrating the... 

A large red shift observed in polar solvents was indicative of the intramolecular charge transfer character of the triplet state. The change of dipole moment accompanying the transition Tj - Tn, as well as rate constants for electron and proton transfer reactions involving the T state of a-nitronaphthalene, were determined. The lower reactivity in polar solvents was attributed to a reduced n-n and increased charge transfer character of the triplet state... 

The complex shown in Figure 3.9 [104] is luminescent in the solid state at 77 K with three emission maxima at 431,448 and 460 nm. The excitation maxima are at 305 and 370 nm. The origin of the luminescence has been attributed to intraligand transitions with contributions of charge transfer character. 

Thermal electron transfer. The high degree of charge-transfer character in [ArH, NO+] complexes is consistent with the fact that a variety of electron-rich aromatic donors undergo reversible electron transfer (in the dark) to form the corresponding cation-radical pair239 (equation 86). 

To illustrate these energy levels, Figure 2.1 shows formaldehyde as an example, with all the possible transitions. The n —> n transition deserves further attention upon excitation, an electron is removed from the oxygen atom and goes into the n orbital localized half on the carbon atom and half on the oxygen atom. The n-n excited state thus has a charge transfer character, as shown by an increase in the dipole moment of about 2 D with respect to the ground state dipole moment of C=0 (3 D). 

It has been suggested that P BChl (where BChl is one of the two monomeric or "accessory BChls that are not part of P) is a transient state prior to P "I (14,16,19), although the evidence supporting this view has been criticized (23, 24) Recent subpicosecond studies find no evidence for P "BChl (8,9) These new results do not preclude some involvement of a monomeric BChl in the early photochemistry, only that P BChl apparently is not a kinetically resolved transient state Perhaps P itself contains some charge-transfer character between its component BChls, or between P and one or both of the monomeric BChls (8,9,25-27) One of the two monomeric BChls apparently can be removed by treatment of the reaction center with sodium borohydride (28) and subsequent chromatography, with no impairment of the primary electron transfer reactions (29) Thus, at present it appears that P I is the first resolved radical-pair state, and it forms with a time constant of about 4 ps in Rps sphaeroides ... 

The optical absorption spectra depend on the solvent. They are red-shifted with the decreasing polarity of the solvents as in EDA, liquid NH3, where they appear at a longer wavelength than in water [49], and blue-shifted in methanol [38]. Moreover, the maximum in NH3 is red-shifted with the increase of temperature. In water, the Ag band is almost unchanged in the range 20-200 °C, while that of Ag2 is markedly shifted to the red [50]. Electron spin echo modulation analysis of Ag in ice or methanol glasses has concluded to a charge transfer character to solvent (CTTS) of the absorption band [51]. 

The interaction of nondegenerate molecular or charge-transfer states is insufficient to describe the stability of photoassociation products of molecules with different electronic energy levels, ionization potentials, and electron affinities. On the other hand, treatments26-26 of the exciplex as a pure charge-transfer state afford a quantitative description of the shift in fluorescence peak with solvent polarity and with electron affinity of the (fluorescent) donor in the same quencher-solvent system (Eq. 13) moreover, estimated values for the dipole moment of the emitting species (Table VI) confirm its pronounced charge-transfer character. 

For the allowed reaction between ethylene and butadiene, D+A can mix into the transition state wave-function, since now and orbitals do overlap (p. 131). As a consequence the barrier is lowered and the transition state acquires some charge transfer character (107). Thus the role of symmetry in... 

The triplet state acidities, pkl, are found to be not much different from ground state pK s. But feterocyclics like o-phenanthroline and quinoline are more basic in triplet state than in ground state, although less basic than in the first excited singlet state. It follows that the singlet transition in these molecules has considerably more charge transfer character than the transition in the triplet state. 

If added substances absoroing at higher frequencies are present the quenching mechanism is visualized to proceed through transient complex formation in the excited state. They are known as exciplexes and have pronounced charge transfer character. Exciplexes may decay radiatively, nonradiatively or lead to reaction products. 

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