Principle of solvatochromism and solvatofluorochromism of organic dyes
Solvatochromism:
Introduction:
When absorption spectra are measured in solvents of different polarity, it is found that the positions,
intensities, and shapes of the absorption bands are usually modified by these solvents. These changes are a
result of physical intermolecular solute–solvent interaction forces (such as ion-dipole, dipole-dipole, dipole-
induced dipole, hydrogen bonding, etc.), which above all tend to alter the energy difference between ground
and excited state of the absorbing species containing the chromophore). The medium influence on
absorption spectra can be considered by comparing the spectral change observed on going from the gas
phase to solution, or simply by changing the nature of the solvent.
Small, side step: A chromophore is generally regarded as any grouping of an organic molecule (sometimes
the whole molecule itself ) which is responsible for the light absorption under consideration. For example,
the C=C (Carbon-carbon double bond) group of ethene or 1-hexene, responsible for their π → π ¿ UV
absorption, is the chromophore of these alkenes. For b-carotene, the whole polyene chain with eleven
conjugated C=C bonds represents the chromophore
The term solvatochromism is used to describe the pronounced change in position (and sometimes intensity)
of a UV/Vis absorption band that accompanies a change in the polarity of the medium. A hypsochromic (or
blue) shift with increasing solvent polarity is usually called negative solvatochromism. The corresponding
bathochromic (or red) shift is termed positive solvatochromism. The solvent effect on spectra, is primarily
dependent on the chromophore and the nature of the transition. The electronic transitions of particular
¿ ¿
interest in this respect are π → π , and n → π , as well as charge-transfer absorptions.
Compounds:
Organic compounds with chromophores containing p-electrons can be classified into three different groups
according to their idealized p-electronic structure: aromatic compounds, polyenes, and polymethines.
Aromatic compounds, polyenes are self-explanatory. Polymethines are also known to us, but let’s recap:
They are conjugated chain molecules with equal bond lengths and charge alternation along the methine
chain. They exhibit the following common structural features:
Of particular interest are the intramolecularly ionic meropolymethine dyes (especially the merocyanines),
whose electronic structure lies somewhere between that of a neutral limiting mesomeric structure without
charge separation and that of a charge-separated zwitterionic form, depending on the nature of X and X` as
well as on solvent polarity. These are systems in which an electron-donating group, D, is linked by a
conjugated system, R, to an electron-accepting group, A. Their intermediate p-electronic structure can be
described in terms of two mesomeric structures, D-R-A ↔ D(+)-R-A(-), as shown on slide.
Its electronic transition is associated with an intramolecular charge-transfer between donor and acceptor
group, producing an excited state with a dipole moment appreciably different from that in the ground state.
It has been established experimentally that only those molecules with p-electrons for which the charge
distribution (and consequently the dipole moment) in the electronic ground state is considerably different
from that in the excited state exhibit a pronounced solvatochromism. Thus, for aromatic compounds,
(without electron donor and/or acceptor groups, like benzene), polyenes (like lycopene, carotinoids),
polyynes (polyacetylenes), and symmetrical polymethine dyes, only a comparatively small solvent
dependence of their UV/Vis absorption spectra is observed.
(EXAPLES OF SMALL SOLVATOCHROMISM)
Not only intramolecularly ionic compounds such as dipolar meropolymethine dyes, but also EPD/EPA
complexes with an intermolecular charge transfer (CT) absorption can exhibit a pronounced
solvatochromism. The CT transition also involves ground and excited states with very different dipole
moments. Charge transfer complexes exhibit charge transfer transitions in which absorption triggers the
transfer of an electron from the donor to the acceptor. As example, when iodine is dissolved in solutions of
donor solvents, the striking purple color of molecular iodine is replaced by a yellow-brown color. This is
because charge transfer complexes like those formed by I2 can absorb light in ways that neither the donor
nor the acceptor can on their own. Specifically, charge transfer complexes exhibit charge transfer bands
(CT bands) in their absorption spectra. In the charge transfer transition the initial partial transfer of charge
from the donor Lewis base to the acceptor Lewis acid in the charge transfer complex is pushed further by
photoexcitation.
Spectroscopic events in CT complexes are fascinating, yet are mostly dominated by chemistry of transitional
metals, so I won’t dive too much into this topic.
Returning to theoretical bases of solvatochromism, lets look at effect different solvents have on absorption
of species we now identified as appropriate for solvatochromic behaviour.
Qualitaive interpretation:
A qualitative interpretation of solvent shifts is possible by considering (a) the momentary transition dipole
moment present during the optical absorption, (b) the difference in permanent dipole moment between the
ground and excited state of the solute, (c) the change in ground-state dipole moment of the solute induced by
the solvent, and (d) the Franck–Condon principle. According to Bayliss and McRae, four limiting cases can
be distinguished for intramolecular electronic transitions in solution:
(1) Nonpolar solute in a nonpolar solvent. In this case, only dispersion forces contribute to the
solvation of the solute. Dispersion forces, operative in any solution, invariably cause a small
bathochromic shift, the magnitude of which is a function of the solvent refractive index n, the
transition intensity, and the size of the solute molecule. Corresponding linear correlations between
bathochromic shift and index n have been observed for aromatic compounds, polyenes, and
symmetrical polymethine dyes.
(2) Nonpolar solute in a polar solvent. In the absence of a solute dipole moment there is no significant
orientation of solvent molecules around the solute molecules, and again a general red shift,
depending on the solvent refractive index n, is expected and observed.
(3) Dipolar solute in a nonpolar solvent. In this case, the forces contributing to solvation are dipole-
induced dipole and dispersion forces. If the solute dipole moment increases during the electronic
transition, the Franck–Condon excited state is more solvated by dipole-solvent polarization, and a
red shift, depending on the solvent refractive index n and the change in solute dipole moment, is
expected. The Franck–Condon excited state is less solvated if the solute dipole moment decreases
during the electronic transition, and a blue shift, again proportional to the two above mentioned
factors, is expected. In the latter case, the resultant shift may be red or blue depending on the relative
magnitude of the red shift caused by polarization and the blue shift.
The Franck–Condon principle states that since the time required for a molecule to execute a vibration
(10(-12) s) is much longer than that required for an electronic transition (10(-15) s), the nuclei of the
chromophore (and of the surrounding solvent molecules) do not appreciably alter their positions during
an electronic transition
(4) Dipolar solute in a polar solvent. Since the ground-state solvation results largely from dipole-
dipole forces in this case, there is an oriented solvent cage around the dipolar solute molecules,
resulting in a net stabilization of their ground state. If the solute dipole moment increases during the
electronic transition, the Franck–Condon excited state is formed in a solvent cage of already partly
oriented solvent dipoles. The better stabilization of the excited state relative to the ground state with
increasing solvent polarity will result in a bathochromic shift. Its magnitude will depend on the
extent of the change in the solute dipole moment during the transition, the value of the solvent dipole
moment, and the extent of interaction between the solute and solvent molecules. This situation is
schematically illustrated
If the dipole moment of the solute decreases during the electronic transition, the Franck–Condon
excited state is formed in a strained solvent cage of oriented dipoles not correctly disposed for its
effcient stabilization. Thus, with increasing solvent polarity, the energy of the ground state is
lowered more than that of the excited state, and this produces a hypsochromic shift. The
superimposed bathochromic shift due to polarization will usually be less, resulting in a net
hypsochromic shift.
For strongly solvatochromic compounds, the observed solvent induced wavelength shifts cannot be
explained only in terms of a change in the permanent dipole moment on electronic transition. The change in
ground-state dipole moment of the solute, induced by the surrounding solvent cage must also be taken into
account. The dipolar solute molecules cause an electronic polarization of the surrounding solvent molecules,
creating a so-called reaction field which affects the solute’s ground-state dipole moment. That is, the
interaction of the dipolar solute molecules with this induced reaction field, due to the total dipole moment
(permanent and induced) of the solvent molecules, may cause an alteration of the electronic structure of the
chromophore. For meropolymethine dyes, this implies that increasing solvent polarity should shift their
electronic ground-state structure from a nonpolar polyenic state (a) towards a zwitterionic polyenic state (c),
depending on the relative electron-acceptor strength of group X and the electron-donor strength of group Y.
Between these two extremes there exists an intermediate state (b), where both mesomeric forms contribute
equally to the molecular ground-state structure. This particular case is referred to as the ideal polymethine
state by Da¨hne or the cyanine limit by Marder, by analogy with symmetrical polymethine dyes, which can
be described as an equal mixture of two degenerate limiting mesomeric forms.
The particular properties of form (b) with respect to its light absorption (longest wavelength), p-bond order
alternation (zero), p-electron density alternation (maximum), optical polarizability (maximum), etc., and
also to other properties are summarized schematically in Scheme on the slide, based on the microstructural
model of solvatochromism for meropolymethine dyes introduced by Da¨hne in 1978.
The effects of such a change in electronic ground-state structure on the position of the absorption band were
calculated by Fo¨ rster in 1939. According to his calculations, the intermediate meropolymethine (b) with
equal contribution of both mesomeric structures (a) and (c) will have the longest-wavelength absorption.
Therefore, a chromophore with a polyene-like electronic structure (a) will exhibit a bathochromic shift with
increasing solvent polarity (positive solvatochromism), whereas a chromophorem with a polymethine-like
electronic structure (b) will show a hypsochromic shift on the same solvent change (negative
solvatochromism).
A particularly interesting solvatochromic merocyanine dye is 1-methyl-4-[(4
oxocyclohexadienylidene)ethylidene]-1,4-dihydropyridine also called Brooker’s merocyanine. First it
exhibits a bathochromic and then a hypsochromic shift of the long-wavelength π → π ¿ absorption band as
the solvent polarity increases. This surprising inverted solvatochromism seems to indicate that the ground-
state electronic structure of this merocyanine dye changes, with increasing solvent polarity, from the
quinonoid structure (a) to the benzenoid structure (c) via the intermediate polymethine-like structure (b).
The more specific solvent-solute interaction can have wildly different nature, so for the sake of brevity I
wont cover them in my presentation. Suffice to say that this question is a topic of many … many scientific
articles.
Application of solvatochromism
For decades solvatochromism had been a phenomenon without any great technical importance in
commercial applications, and was used largely to characterise solvents or to understand the excitation
behaviour of chromogenic solutes including commercial azo dye models. However, since the 90s there has
been a rapid growth in the use of optical probes and sensors, an area where solvatochromic effects now play
an important role, and this has led to a renewed interest and expansion in research on solvatochromism.
Analysis of Liquids
An obvious application of solvatochromism is the measurement of concentrations of small amounts of polar
molecules in nonpolar environments, like for example methanol in naphtha. Fuel oil is a key market, as the
various fractions are often ‘‘marked’’ with solvent dyes to ease their identification for tax purposes.
With the increase in the use of alcohols as fuels, both on their own and in admixture with gasoline, it has
been necessary to have a rapid means of measuring their quality
Dyes 1–4 were successful as polarity probes in gasoline– ethanol mixtures, and were thus capable of quickly
quantifying amounts of ethanol in gasoline samples. In the case of pyridiniophenolate 2, solutions show a
blue–green color in gasoline and are violet in ethanol, passing through a green–blue color in gasoline with
25% of ethanol. These colour changes allow the naked-eye detection of the presence of ethanol in gasoline
and the development of an analytical method for the determination of the quality of the fuels.
Dimroth and Reichardt have proposed a solvent polarity parameter, ET(30), based on the transition energy
for the longest-wavelength solvatochromic absorption band of the pyridinium N-phenolate betaine dye (1)
also called Reichardt's dye (Betaine 30). According to eq. on slide, the ET(30) value for a solvent is simply
defined as the transition energy of the dissolved betaine dye (1) measured in kcal/mol.
To date, the betaine dye (1) holds the world record in solvatochromism with a direct experimentally
observed hypsochromic shift of ∆λ = -357 nm (for a solvent change from diphenyl ether to water). Owing to
this exceptionally large displacement of the solvatochromic absorption band, the ET(30) values provide an
excellent and very sensitive characterization of the polarity of solvents. High ET(30) values are
corresponding to high solvent polarity. A remarkable feature of these solution colour changes is that nearly
every colour of the visible spectrum can be obtained by employing suitable binary mixtures of solvents of
different polarity.
Solvatochromic Probes
Solvatochromic probes have found applications in polymer characterisation, where they can be used to look
for localised polar features at the molecular level. Two distinct approaches can be adopted, where the
chromophore can be part of the polymer of the chain, or the chromophore can be dissolved in a solvent and
then this solution used to penetrate the polymer matrix. In the first case, the environment is fixed and so the
probe is unable to choose a preferred site for its colour change, but can give information of chain orientation
etc. In the second, the probe is mobile and will seek out the most favourable site over a period of time,
enabling areas of differing polarity within the polymer to be identified. Incorporation of solvatochromic
dyes in polymers is also used to construct commercially useful polymer bound sensors. When coupled with
fibre optics, these offer a safe way of examining flammable solvents for their composition and levels of
liquid impurities.
The extreme sensitivity of the visible absorption spectrum to small changes in the surrounding medium has
made Reichardt's dye based probes useful in the study of micellar systems, microemulsions and
phospholipid bilayers, model liquid membranes, polymers, organic-inorganic polymer hybrids, sol-gel
matrices, surface polarities, and the retention behaviour in reversed-phase liquid chromatography.
Figure 4 demonstrates that Reichardt's dye can be used as internal probe for the micellar aggregation
behavior of surfactants such as homologous tetraalkylammonium betaines in aqueous solution. The
micellisation with increasing surfactant concentration can easily be followed UV/vis spectroscopically by
means of Reichardt's dye: the ET(30) values strongly decrease after reaching the critical micelle
concentration (CMC) due to the transfer of dye molecules from an aqueous into a micellar
microenvironment.
Solvatochromic dyes have also been used for the determination of the surface polarity of zeolite cages of
solid poly(a-amino acids), as well as of native polysaccharides (cellulose, glycogen, amylopectin, amylose,
starch, etc.) and various cellulose ester derivatives. When solvatochromism is used to characterise
empirically the surface properties of moderately strong solid acids, including silicas, aluminas and
aluminosilicates, the chromic phenomenon has been called ‘‘sorptiochromism’
A remarkable example is the variation in surface polarity of thermally treated, mesoporous, commercially
available silica (“Kieselgel 60”) as shown in Fig. 5. Initial heating of “Kieselgel 60” causes a rapid loss of
mass due to the removal of loose hydrogenbonded water. Further heating results in a loss of silanol groups
by a condensation reaction producing more and more less dipolar siloxane bridges. The loss of surface water
corresponds well with the simultaneous decrease of surface polarity as shown by the En/t values, determined
by diffuse reflectance UV/vis spectroscopy of betaine dye 1 adsorbed on the silica surface. The En/t value
drops from 0.88 for wet “Kieselgel 60” to a final value of 0.72 for the dehydrated probe.
Solvatofluorochromism
When excited states of a molecule are created in solution by continuous or flash excitation, the excited-state
molecule interacts to a varying degree with the surrounding solvent molecules, depending on their polarity,
before returning to the ground state. These excited-state solute/solvent interactions found in fluorescent
molecules are often reflected in the spectral position and shape of the emission bands as well as in the
lifetimes of the excited-state molecules and is called – solvatofluorochromism.
When considering the solvent dependence of the position of emission bands, the finite relaxation time Tr for
the rearrangement of the solvent molecules surrounding the solute molecule in the Franck–Condon excited
state and the finite lifetime Te of the molecule in the excited state have to be taken into account.
In the case of tR>>te, the emission will occur before any rearrangement of solvent molecules in the
solvation shell takes place. The initial state of the emission process is the Franck–Condon excited state and
the final state is the equilibrium ground state. Hence, the wavenumber of emission will be equal to the
wavenumber of the corresponding absorption (Taking in to account slight Stock`s shift). In liquid solutions,
the rotational relaxation time tR for the solvent molecules is in the range 10(-12) to 10(-10) s at room
temperature; the lifetime te of an excited singlet state is of the order of 10(-8) s. Hence, under these
circumstances tR>>te will be generally valid. tR increases strongly with decreasing temperature, while te is
only slightly temperature dependent. Therefore, at lower temperatures the case where tR=te can occur. In
solid solutions tR<<te is the norm. In the case of tR<<te, reorientation of the solvent molecules can take
place after electronic excitation and a relaxed excited state is obtained in which another solvation
equilibrium has been established. It is from this equilibrium state that fluorescence occurs at room
temperature. By analogy, there is a Franck–Condon ground state after emission, which persists
momentarily until the solvent molecules reorganize to the equilibrium arrangement for the ground state.
A general explanation of solvent effects on fluorescence spectra is based on the differential solvation of the
fluorescent molecules in their ground and excited states, mediated by the various non-specific and specific
intermolecular forces acting between the solute and solvent. When the ground and excited states of an apolar
fluorophore differ only in their polarizabilities and not in their dipolarities, then only solute/solvent
dispersion interactions exist and rather small or no solvent-induced band shifts are observed. As an example,
for benzo[a]pyrene, an apolar planar aromatic hydrocarbon with negligible dipole moments, no discernible
solvent dependence of the Stokes shift was observed in 15 solvents of different polarity.
However, most fluorophores undergo an intramolecular charge transfer upon excitation so that usually
μe > μg . In such cases, the relaxed excited state S1 will be energetically stabilized relative to the ground state
S0 and a significant red shift of the fluorescence band will be observed. The stronger the solute/solvent
interaction, the lower the energy of the excited state, and the larger the red shift of the emission band and the
corresponding Stokes shift.
An illustrative example of solvent influence on absorption and emission spectra is given by the following
positive solvatochromic laser dye 7-dialkylamino-4-(trifluoromethyl)coumarin (coumarin C153), in which
rotation of the amino group is restricted by incorporating it into a hexahydroquinolizine ring.
With increasing solvent polarity, both absorption and emission bands undergo a bathochromic shift, the
latter being more pronounced than the former. This indicates an intramolecular charge-transfer (ICT)
absorption of the less dipolar ground-state molecule with (a) as the dominant mesomeric structure, leading to
highly dipolar excited state molecule with (b) as the prominent structure. It is this planar ICT excited-state
molecule from which the emission occurs. Increasing solvent polarity stabilizes the ICT excited-state
molecule relative to the ground-state molecule with the observed red shift of the fluorescence maximum as
the experimentally observed result.
The existence of two interconvertible excited-state molecules can lead to a dual, variable solvent-dependent
fluorescence. This dual fluorescence was first discovered by Lippert, using 4-(dimethylamino)benzonitrile
(DMABN) as the fluorescent compound, and then interpreted by Grabowski. The dual fluorescence of
DMABN consists of emission from an initially populated locally excited (LE) S1 state and from an ICT
state. In nonpolar solvents, only a single fluorescence band is observed from the LE state. In polar solvents,
the LE state reacts further to a stable ICT state, which gives rise to a second fluorescence band, abnormally
large red-shifted from the LE emission. The precise molecular structure of the ICT state of DMABN is still
under debate.
Particularly well studied examples of another solvent-dependent dual fluorescence are 6-(arylamino)-2-
naphthalene sulfonates (ANS). (np = nonplanar; ct = charge transfer)
Application of solvatofluorochromism
A small selection of strongly solvatochromic fluorophores, recommended as solvent polarity probes because
of their large solvent-induced shifts of the long-wavelength emission band, is given in Scheme 6-2 (Next
slide). An extreme example of solvent-dependent fluorescence of an ICT excited-state molecule is shown by
1-phenyl-4-(4-cyano-1-naphthylmethylene)piperidine, a rod-shaped molecule containing electron-donor (D)
and -acceptor groups (A) separated by an elongated cycloalkyl spacer. This molecule is also called
“Fluoroprobe’’
Also, fluorescence measurements on short-lived (<1 ns) and long-lived (>10 ns) electronically excited
organic molecules in binary solvent mixtures have been used to study the phenomenon of selective or
preferential solvation of dipolar solute molecules.
