SOLVENT SHIFTS IN CHARGE-TRANSFER SPECTRA. INFLUENCE OF DONOR STRENGTH

1966 ◽  
Vol 44 (20) ◽  
pp. 2405-2407 ◽  
Author(s):  
H. M. Rosenberg ◽  
E. Eimutis ◽  
D. Hale

The charge-transfer transition energies for a series of methylbenzene–tetracyanoethylene complexes in four solvents are reported. The charge-transfer transition energies are found to decrease with increasing solvent refractive index. The magnitude of the decrease appears to be a function of donor strength. It is inferred that the excited state dipole moment decreases with increasing donor strength for these complexes.

1975 ◽  
Vol 30 (3) ◽  
pp. 287-291 ◽  
Author(s):  
I. Gryczyński ◽  
A. Kawski

A variation of the temperature changes the static dielectric constant (ε) and the refractive index (n) of solvents and, in conjunction with the measurement of solvent shifts of absorption and fluorescence maxima, allows the investigation of dipole moment changes of solutes in the excited state. For this purpose, investigations of the temperature dependences of ε and n of some pure and mixed solvents of different polarities have been made. It is found that the excited dipole moments of indole, 1,2-dimethylindole, 2,3-dimethylindole and tryptophan obtained from the shifts of the fluorescence maxima in mixed solvents at high temperatures are in good agreement with those obtained in other ways.


2011 ◽  
Vol 83 (10) ◽  
Author(s):  
S. G. Choi ◽  
H. T. Yi ◽  
S.-W. Cheong ◽  
J. N. Hilfiker ◽  
R. France ◽  
...  

2015 ◽  
Vol 19 (01-03) ◽  
pp. 527-534
Author(s):  
Kamlesh Awasthi ◽  
Hung-Yu Hsu ◽  
Hung-Chu Chiang ◽  
Chi-Lun Mai ◽  
Chen-Yu Yeh ◽  
...  

Polarized electroabsorption (E-A) spectra of highly efficient porphyrin sensitizers (YD2 and YD2-oC8) have been measured in benzene solution. Polarized E-A spectra of these push–pull porphyrins embedded in poly(methyl methacrylate) films or sensitized on TiO 2 films are also observed. Based on the analysis of the E-A spectra, the magnitude of the electric dipole moment both in the ground state and in the lowest excited state have been evaluated in solution and in solid films. The electric dipole moment in the excited state of these compounds is very large on TiO 2 films, suggesting the interfacial charge transfer on TiO 2 surface following photoexcitation of porphyrin dyes. The electric dipole moment in the excited state evaluated from the E-A spectra is very different from the one evaluated from the electrophotoluminescence spectra on TiO 2, suggesting that the strong local field of TiO 2 films is applied to the fluorescing dyes attached to TiO 2 films.


2003 ◽  
Vol 81 (6) ◽  
pp. 567-574
Author(s):  
Dustin Levy ◽  
Bradley R Arnold

Time-resolved linear dichroism spectroscopy has been used to study the influence of solvent on the charge transfer complex formed between hexamethylbenzene and 1,2,4,5-tetracyanobenzene. It was shown that cyano-substituted solvents induce a 1500 cm–1 increase in the charge transfer transition energies relative to those observed in chlorinated solvents. Furthermore, the angle between the charge transfer absorption transition moments and the photochemically produced radical anion absorption transition moment, after relaxation, has been measured for this complex in several solvents. A simple model was used to correlate the angles measured using time-resolved linear dichroism spectroscopy with the extent of localized excitation mixed into the charge transfer transitions. These measurements reveal that different charge transfer transitions borrow intensity from the localized excitation to different extents. By using different excitation wavelengths, the partitioning of the borrowed intensity among the charge transfer transitions of this complex could be evaluated for the first time.Key words: 1,2,4,5-tetracyanobenzene, hexamethylbenzene, donor–acceptor complex, photoinduced electron transfer, photoselection.


1983 ◽  
Vol 87 (22) ◽  
pp. 4348-4351 ◽  
Author(s):  
Daniel D. Altenloh ◽  
B. R. Russell ◽  
Linda Rae Ashworth

1971 ◽  
Vol 55 (9) ◽  
pp. 4668-4669 ◽  
Author(s):  
Robin M. Hochstrasser ◽  
J. W. Michaluk

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