Solvatochromic changes

The cluster formation is also reversible [80]. After the solvatochromic changes take place at a given acetonitrile composition, decreasing the acetonitrile composition by adding toluene to the mixture can change the solution color and absorption spectrum back to those of the fullerene monomer. The absorption spectrum of the cluster solution also changes upon dilution. A gradual... 

Chloroform is a good solvent to both the hydrophobic backbone and Ihe hydrophilic pendants. The polymer chains may be well solvated by the solvoit and take an extended planar conformation, in which the polyacetylene backbone is better conjugated. Toluene is, however, a poor solvent of the hydrophilic pendants. To minimize the exposure of their pendants to the un vorable hydrophobic solvent environment, the polymer chains may take a coiled non-planar conformation, in which the polyene bacldione may be less conjugated. Since the conformational change is induced by the noncovalent solvent-polymer interaction, it is easy to understand why the solvatochromic change is continuous and reversible. 

Although inverted solvatochromism in betaines has been widely studied, no test clearly exposing the abmpt change from bathochromic solvatochromism to hyp-sochromic solvatochromism has so far been devised. Finding that the dipolarity of 1-chlorobutane increases markedly with decreasing temperature" allowed us to unambiguously expose this solvatochromic change" (see Fig. 9.3.13). 

Solvent Influence. Solvent nature has been found to influence absorption spectra, but fluorescence is substantiaHy less sensitive (9,58). Sensitivity to solvent media is one of the main characteristics of unsymmetrical dyes, especiaHy the merocyanines (59). Some dyes manifest positive solvatochromic effects (60) the band maximum is bathochromicaHy shifted as solvent polarity increases. Other dyes, eg, highly unsymmetrical ones, exhibit negative solvatochromicity, and the absorption band is blue-shifted on passing from nonpolar to highly polar solvent (59). In addition, solvents can lead to changes in intensity and shape of spectral bands (58). 

The preceding empirical measures have taken chemical reactions as model processes. Now we consider a different class of model process, namely, a transition from one energy level to another within a molecule. The various forms of spectroscopy allow us to observe these transitions thus, electronic transitions give rise to ultraviolet—visible absorption spectra and fluorescence spectra. Because of solute-solvent interactions, the electronic energy levels of a solute are influenced by the solvent in which it is dissolved therefore, the absorption and fluorescence spectra contain information about the solute-solvent interactions. A change in electronic absorption spectrum caused by a change in the solvent is called solvatochromism. 

Experimental results corroborate that shifts of 1.2 eV are always present if any of the variables acting on the electrochemical process are changed the solvent, the salt, or the temperature of work. We cannot attribute the observed shift to solvatochromic, counter-ion-chromic, or thermochromic effects taking place inside the film during oxidation-reduction processes. So, as predicted, these shifts are a consequence of the way the chains store or relax energy through conformational changes stimulated by electrochemical oxidation or reduction, respectively. 

It should be born in mind, however, that the activation parameters calculated refer to the sum of several reactions, whose enthalpy and/or entropy changes may have different signs from those of the decrystalUzation proper. Specifically, the contribution to the activation parameters of the interactions that occur in the solvent system should be taken into account. Consider the energetics of association of the solvated ions with the AGU. We may employ the extra-thermodynamic quantities of transfer of single ions from aprotic to protic solvents as a model for the reaction under consideration. This use is appropriate because recent measurements (using solvatochromic indicators) have indicated that the polarity at the surface of cellulose is akin to that of aliphatic alcohols [99]. Single-ion enthalpies of transfer indicate that Li+ is more efficiently solvated by DMAc than by alcohols, hence by cellulose. That is, the equilibrium shown in Eq. 7 is endothermic ... 

Contact diffusion Reaction with a change Noncontact Solvatochromism ... 

When Ajx = /positive solvatochromism resulting in the red shift of transitions otherwise, when A/r is negative, the spectra move to the blue and that is the case of negative solvatochromism. As follows from this expression, the change of dipole moments A/r during electronic transition is a necessary condition for observed solvatochromic shift the more this difference -the stronger is the solvatochromic shift. The second important parameter is the local... 

In addition to the described above methods, there are computational QM-MM (quantum mechanics-classic mechanics) methods in progress of development. They allow prediction and understanding of solvatochromism and fluorescence characteristics of dyes that are situated in various molecular structures changing electrical properties on nanoscale. Their electronic transitions and according microscopic structures are calculated using QM coupled to the point charges with Coulombic potentials. It is very important that in typical QM-MM simulations, no dielectric constant is involved Orientational dielectric effects come naturally from reorientation and translation of the elements of the system on the pathway of attaining the equilibrium. Dynamics of such complex systems as proteins embedded in natural environment may be revealed with femtosecond time resolution. In more detail, this topic is analyzed in this volume [76]. 

Molecular rotors are useful as reporters of their microenvironment, because their fluorescence emission allows to probe TICT formation and solvent interaction. Measurements are possible through steady-state spectroscopy and time-resolved spectroscopy. Three primary effects were identified in Sect. 2, namely, the solvent-dependent reorientation rate, the solvent-dependent quantum yield (which directly links to the reorientation rate), and the solvatochromic shift. Most commonly, molecular rotors exhibit a change in quantum yield as a consequence of nonradia-tive relaxation. Therefore, the fluorophore s quantum yield needs to be determined as accurately as possible. In steady-state spectroscopy, emission intensity can be calibrated with quantum yield standards. Alternatively, relative changes in emission intensity can be used, because the ratio of two intensities is identical to the ratio of the corresponding quantum yields if the fluid optical properties remain constant. For molecular rotors with nonradiative relaxation, the calibrated measurement of the quantum yield allows to approximately compute the rotational relaxation rate kor from the measured quantum yield [Pg.284]

It is possible, however, that the electrochromic response of some styrylpyridi-nium probes, for example, RH421 (see Fig. 2), is enhanced by a reorientation of the dye molecule as a whole within the membrane. There is a steep gradient in polarity on going from the aqueous environment across the lipid headgroup region and into the hydrocarbon interior of a lipid membrane. Therefore, any small reorientation of a probe within the membrane is likely to lead to a change in its local polarity and hence a solvatochromic shift of its fluorescence excitation spectrum. Such a... 

Mukherjee, S., Chattopadhyay, A., Samanta, A. and Soujanya, T. (1994). Dipole-moment change of Nbd group upon excitation Studied using solvatochromic and quantum-chemical approaches - Implications in membrane research. J. Phys. Chem. 98, 2809-2812. 

Finally, concerning dialkylpolysilanes, it is interesting to note that the solid-state (film) UV spectral profile of the thermochromism exhibited by 49,157 shown in Figure 28, almost exactly matches that of the solvatochromism (see Figure 16 above). This indicates that the before and after conformations are essentially the same and that the reduction of temperature or addition of HFIP are responsible for similar conformational changes in the polymer an abrupt straightening of the polysilane backbone. 

The marked changes in the carbonyl IR bands accompanying the solvent variation from tetrahydrofuran to MeCN coincide with the pronounced differences in colour of the solutions. For example, the charge-transfer salt Q+ Co(CO)F is coloured intensely violet in tetrahydrofuran but imperceptibly orange in MeCN at the same concentration. The quantitative effects of such a solvatochromism are indicated by (a) the shifts in the absorption maxima and (b) the diminution in the absorbances at ACT. The concomitant bathochromic shift and hyperchromic increase in the charge-transfer bands follow the sizeable decrease in solvent polarity from acetonitrile to tetrahydrofuran as evaluated by the dielectric constants D = 37.5 and 7.6, respectively (Reichardt, 1988). The same but even more pronounced trend is apparent in passing from butyronitrile, dichloromethane to diethyl ether with D = 26, 9.1 and 4.3, respectively. The marked variation in ACT with solvent polarity parallels the behaviour of the carbonyl IR bands vide supra), and the solvatochromism is thus readily ascribed to the same displacement of the CIP equilibrium (13) and its associated charge-transfer band. As such, the reversible equilibrium between CIP and SSIP is described by (14), where the dissociation constant Kcip applies to a... 

Cross-reactive sensing arrays were developed to detect odors and vapors in an artificial nose manner. Solvatochromic dyes such as Nile Red are adsorbed on the surface or embedded into various polymeric or porous silica beads. The beads respond to analyte vapor by a change in fluorescence maxima or/and intensity due to changes of polarity inside the bead. A portable instrument and preliminary field test for the detection of petroleum products was recently described [106]. 

Solvatochromism refers to changes in the electronic state of the solute (specifically, the solute s electronic state transition energy) caused by the solvent. 

A number of poly(arylene vinylene) (PAV) derivatives have been prepared. Attachment of electron-donating substituents, such as dimethoxy groups (structure 19.3), acts to stabilize the doped cationic form and thus lower the ionization potential. These polymers exhibit both solvatochromism (color changes as solvent is changed) and thermochromism (color is temperature-dependent). 

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