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Chemical Physics 288 (2003) 309–325 www.elsevier.


Solvent influence on absorption and fluorescence spectra of merocyanine dyes: a theoretical and experimental study
I. Baraldi, G. Brancolini 1, F. Momicchioli *, G. Ponterini, D. Vanossi
Dipartimento di Chimica, Universita  di Modena e Reggio Emilia, Via Campi 183, I-41100 Modena, Italy Received 8 November 2002

Abstract The solvaton–CS INDO model, previously successfully used to describe the solvatochromic properties of merocyanines, has been extended to the study of the solvent influence on the fluorescence spectra (fluorosolvatochromism) of these dyes. A ketocyanine (M1) and a stilbazolium betaine (M2) were chosen as representatives of positively and negatively solvatochromic behaviours, respectively. The gap of experimental knowledge concerning the emission properties of M2 was filled by a spectrofluorometric analysis in a set of solvents covering a large range of the ET ð30Þ scale. Solvato- and fluorosolvatochromism were described by calculating the S0 ðeq:Þ ! S1 ðFranck–CondonÞ and S1 ðeq:Þ ! S0 ðFranck– CondonÞ transition energies as a function of a polarity factor related to the static dielectric constant of the solvent, and ranging from 0 to 1. The absorbing S0 ðeq:Þ and emitting S1 ðeq:Þ units (solute molecule + solvent cage) were approximated using the S0 and S1 geometries of the unsolvated molecule and the respective charge distributions fitted to the current value of k ðeÞ. The calculation results fully confirm that S0 and S1 states of merocyanines can be viewed as a mixture of a neutral and a zwitterionic structure whose composition is controlled by the solvent polarity. The plots of the calculated spectral data (absorption and emission maxima and corresponding Stokes shifts) vs k ðeÞ are in fairly good agreement with those of N the experimental data over almost the entire range of the normalized ET values, thus showing that specific solvent interactions are at least partly simulated within the solvaton–CS INDO scheme. The methodological prerequisites for a correct prediction of solvatochromic shifts are recalled with reference to previous conflicting theoretical interpretations. Ó 2003 Published by Elsevier Science B.V.

1. Introduction We have recently shown [1,2] that solvent effects on both ground-state properties and absorption spectra of classic donor–acceptor dyes, such as
* Corresponding author. Tel.: +39-59-2055081; fax: +39-59373543. E-mail address: (F. Momicchioli). 1 Present address: Dipartimento di Chimica ‘‘G.Ciamician’’, Universit a di Bologna, Via F.Selmi 2, I-40126 Bologna, Italy.

merocyanines, can be fairly well accounted for within the CS INDO scheme [3]. Briefly, the solute–solvent interactions were described by the simple solvaton model [4] and were incorporated in the CS INDO Hamiltonian according to previous basically equivalent all valence electron SCF approaches [5–11]. Our procedure, however, is characterized by a peculiar modelling of the solvaton set representing the polarized solvent surrounding the solute. We followed the basic widely accepted idea that the electronic structure of

0301-0104/03/$ - see front matter Ó 2003 Published by Elsevier Science B.V. doi:10.1016/S0301-0104(03)00046-6

On the other hand. 1. 1. The zwitterionic form ‘‘exists’’ only in the presence of a polar medium and its electronic spectrum can be calculated only using the solvent-polarized MOs.15.6. the majority of the cited theoretical studies [1. we were able to provide a satisfactory description of both the positive solvatochromism of two vinylogous streptomerocyanines (Fig. [16] using the self-consistent reaction field (SCRF) model within the INDO method. related to variations of the resonance hybrid composition. / Chemical Physics 288 (2003) 309–325 merocyanines can be described at the p level in terms of resonance between neutral and chargeseparated forms (Fig. 1). 2. n ¼ 2. 1) and that the solvatochromic behaviour can be traced back to the relative weights of the two structures in the ground state and their change upon vertical transition to the electronic excited state [12. and hence may effectively account for the p-electron redistribution induced by the solvent polarity. M2: 40 -hydroxy-1-methylstilbazolium betaine. obtained in the polar medium. Morley [14] predicted the opposite trend combining AM1 structure optimization in the presence of the ‘‘solvent’’ and gas phase CNDOVS calculation of the transition energy for the solventdistorted molecular geometry. as some authors did by the middle of the 1990s [14.3. M2). The same twofold problem had previously been addressed by Albert et al.2]). In a more realistic way. As a matter of fact. the electronic structure yielded by an MO calculation corresponds to a mixture of VB structures.8-tetraen-5-one.2. Investigated compounds. Fig. but no choice of the cavity-size parameter had yielded a reasonable prediction for the two opposite solvatochromic behaviours (for more details see [1.6. absorbs at the red of the neutral (quinonoid) form prevailing in non-polar medium.15. Neutral and charge-separated mesomeric structures of simple streptopolymethine merocyanines.2]. trends were qualitatively well reproduced only by Klamt [17] using the AM1/COSMO method.10. Using such a solvaton set within the CS INDO CI scheme [1. no matter what geometry is used. were also predicted. the two solvatochromic Fig. Independently of the specific (continuum) solvent model.15]. Such a scheme stresses the key role of the p-electron distribution and suggests that an effective solvent field must be first of all capable of correctly controlling the drift of p-electrons from the donor ðR2 NÞ to the acceptor (CO) group.310 I. A very elementary way to simulate a polarized environment is to position one or more point charges at one or either end of the chromophore system.17] reproduced qualitatively the negative solvatochromism of M2. Baraldi et al. is questionable since. depending on the nature of the donor and acceptor groups. with p net charge Qp . To our knowledge. 2. The so-defined solvaton set reflects the composition of the resonance hybrid (Fig. a fictive particle with charge – Qp interacting with all electron and core charges of the solute according to BornÕs law. however.9-di-(N-phenyl-N-methyl)-4.17] predicted solvato- . Reasonable structural variations with solvent polarity.dimethylene-nona-1. Other theoretical studies introducing the solvent dielectric field through either a set of point charges [14. M1: 1. This result was interpreted by Morley as evidence that the zwitterionic (benzenoid) form. 4) and the large negative solvatochromism of stilbazolium betaine [13] (Fig.13].15] or the virtual charge model [10] dealt only with stilbazolium betaine which has attracted great attention in relation to its uncommonly large negative solvatochromism and the much-discussed solvatochromic reversal at low medium polarity [18]. following the solvaton model [4] we associated with each atom of the conjugated system.2. all calculations complying with this condition [1.10. Such interpretation.

is that it formally leaves out specific solvent interactions. our solvaton–CS INDO scheme appears to have two main advantages: (i) both ground and excited-state properties are calculated for the solute molecule embedded in the solvent. A disadvantage. where the solvent interaction is introduced essentially through a variation of the diagonal elements of the Fock matrix corresponding to the AOÕs of the p system. for example. 2). the solvaton–CS INDO scheme was subjected to further validation by studying the solvent effects on the fluorescence spectra (fluorosolvatochromism) 3 which have to date received relatively little attention from a theoretical point of view. However. the absorption of which is characterized by one of the strongest negative solvatochromisms ever observed. the solvent dependence of the position of the absorption and fluorescence bands will be termed solvatochromism and fluorosolvatochromism. In principle. 2 tra of these dyes in solvents of different polarities are available ([25].I. respectively. we simply used S0 and S1 geometries optimized in the gas-phase approximation and calculated the S0 ðeq:Þ ! S1 ðFranck–CondonÞ and S1 ðeq:Þ ! S0 ðFranck– CondonÞ transition energies as functions of the solvent polarity using solvaton sets reflecting the p net charges of S0 ðeq:Þ and S1 ðeq:Þ.1. This may explain the positive solvatochromism erroneously predicted for M2 in [16] when using physically reliable values of the cavity radius. shared by all continuum models.27]. On the other hand. Abundant experimental data concerning the absorption specA calculation procedure like the Morley one was applied in [16] where INDO–SCRF optimized geometries were used in gas phase INDO/S type calculations of the spectra. (ii) M2. (ii) the use of a solvaton set reflecting the net p-electron charges enables the solvent interaction to be modelled in keeping with the VB description of the electronic structure of the solute. and the solventinduced spectral shifts of both absorption and fluorescence emission were investigated. In summary. 2 Qualitatively equivalent results were obtained by Benson and Murrell [19] within an SCF p-electron treatment where the effect of solvent was simulated by suitable choice of one-centre core and electron repulsion integrals for the nitrogen and oxygen atoms. The calculation results will first be thoroughly analysed by reference to the basic characteristics of the theoretical model and will then be subjected to a detailed comparison with experimental observations in solvents covering the whole scale of solvation power. Materials. such effects can be accounted for only within semicontinuum type theories [20. H ¼ HOMO. to our knowledge solvent effects on the fluorescence spectra have been reported only for M1 [26. our very simple scheme.21] or fully discrete type approaches as. those based on statistical mechanics techniques [22–24]. instrumentation and details of experiments M2 (4-[(1-methyl-4(1H)-pyridinylidene)ethylidene]-2. / Chemical Physics 288 (2003) 309–325 311 chromic shifts in qualitative agreement with experiment. Thus. a ketocyanine dye (M1) and stilbazolium betaine (M2) (Fig. It will be shown that both the solvatochromic and fluorosolvatochromic behaviours of M1 and M2 are qualitatively well described within the solvaton–CS INDO scheme. L ¼ LUMO) state. the experimental data as a whole show that: (i) M1 exhibits strong positive solvatochromism in both absorption and emission [25–27]. In the present work. In principle. In practice. From the above brief survey. 3 Hereafter. may implicitly account for specific solvent interactions as first argued by Benson and Murrell [19]. Experimental investigation on dye M2 2. The theoretical interpretation of the entire body of experimental evidence was undertaken by applying the solvaton–CS INDO method within a usual scheme where the fluorescence emission takes place from the equilibrium geometry of the lowest excited singlet state reached very quickly after vertical S0 ! S1 excitation of the equilibrium ground state.5-cyclohexadien-1-one) was purchased from . this should require geometry optimization of the solvated solute molecule in both the ground state S0 and the emitting S1 (pH pà L. Baraldi et al. As test compounds we chose two merocyanines. 2. we first of all carried out an experimental exploration of the absorption and emission solvatochromism of M2. features a markedly weaker negative fluorosolvatochromism. and references cited therein). respectively [25].

the absorption spectrum of M2 shows a change in shape on moving from low-polarity solvents. / Chemical Physics 288 (2003) 309–325 Aldrich and was used as received. The suitability of stilbazolium betaine M2 as test compound for negative solvatochromism in both absorption and fluorescence required on the contrary further experimental investigation. where a pronounced structure is observed. in the present work we replaced the streptomerocyanines (Fig. Thus. However. between 0. the theoretical study (Section 3) was based on the abundant experimental data reported in the literature [25–27].1–0.15 for fluorescence measurements. Baraldi et al. where the structure is blurred out. In [1. where r refers to the reference. Fluorescence quantum yields ðUF Þ were determined in methanol and water with respect to cresyl violet in methanol (UF ¼ 0:65 [28]) and eosin in methanol (UF ¼ 0:60 [29]) according to the usual expression: UF ¼ UF.r ðA=Ar Þðn2 =n2 rÞ ðODr =ODÞ. wide monochromator slits were used (6–8 nm spectral resolution) to improve the signalto-noise ratio. For the same reason. to highly polar and protic solvents. Inner filter effects were deemed negligible on both emission spectra and fluorescence quantum yields because of the optical thinness of the samples employed and of the low to very low spectral overlap between absorption and emission. As is well known. Previous theoretical and photophysical studies [30–32] have pointed out that in general streptomerocyanine derivatives have no such characteristics because of the presence of lowest-lying npà states and the occurrence of fast trans–cis isomerization following direct S0 ! S1 ðpH pà L Þ excitation. Absorption spectra were recorded on a Perkin– Elmer k15 spectrophotometer.2. at least. The polar and hygroscopic ones were treated with solid KOH so as to dissolve the M2 betaine in the unprotonated form. All experiments were carried out at room temperature (18–21 °C). Due to the very weak fluorescence emission of M2. On the other hand. Results and discussion The choice of test merocyanine dyes suitable to check thoroughly the capability of the solvaton– CS INDO method of accounting for solvent effects on both absorption and fluorescence spectra was not a trivial affair. Similar observations had led other authors to question the reliability of any .2]. For merocyanines closely related to M2. while a Spex-Jobin Yvon Fluoromax 2 spectrofluorometer was employed for the fluorescence measurements. Emission and excitation spectra were corrected for the instrumental spectral response.312 I. 2. In both cases the intense colour band is due to the lowest p ! pà (essentially pH ! pà L ) transition and the observed solvent shifts are not affected by the presence of any forbidden npà state at low energies. measurements in water were carried out in 10À2 M NaOH.1 and 1 (corresponding to sample concentrations from 3  10À6 to 3  10À5 mol dmÀ3 ) for absorption measurements. In the latter. the structured spectra observed in different solvents of relatively low polarity were attributed to the presence in solution of two variously identified species ([33]. Maximum optical densities were. 2) were taken as typical dyes with strong positive and negative solvatochromism. and references cited therein). In this case. 1) with the ketocyanine M1 (Fig. typically. All solvents (Merck and Lab-Scan) were of spectroscopic grade and were dehydrated with activated molecular sieves before use.2] simple streptomerocyanines (Fig. two different wavelengths on the high-energy side of the absorption band. in compliance with the previous studies limited to effects on the absorption spectra [1. we needed two compounds characterized by opposite solvatochromisms. A are the areas of the corrected emission bands. and around 0. respectively. 1) and stilbazolium betaine (M2 in Fig. dye M2 exhibits a very large negative solvatochromism in absorption ($6500 cmÀ1 on going from CHCl3 to H2 O solution) [25]. in order that the study may be extended to fluorosolvatochromism the test compounds should be characterized by an efficiently emitting lowest-lying pH pà L state. 2) which is known to be an efficient fluorophore exhibiting large red shifts in both absorption and emission spectra upon increasing the solvent polarity [25]. n are the solvent refractive indexes and the optical-density (OD) ratios at the excitation wavelengths were adjusted to unity. especially in low-polarity solvents. each sample was excited at. First.

we found the fluorescence quantum yield of M2 to be only 2:0  10À3 in methanol. even though weakly fluorescent. Moreover. Absorption (full line). apart from a weak solvent Raman band (around 560 nm in Fig. fluorescence excitation (dashed line.1 (water). 1:5  10À3 in water and even lower values were measured in solvents of low polarity. direct S0 ! S1 excita- tion of unprotonated stilbazolium betaine M2 does not result in trans–cis isomerization but it is followed by fast thermally activated relaxation (1. For this purpose. The emission and excitation spectra showed only a very modest dependence on. 3000 cmÀ1 from the monitoring wavenumber. kexc ¼ 580 nm) spectra of M2 in a 1:1 dichloromethane–toluene mixture. reflecting only Fig. we carried out a spectrofluorometric analysis in a 1:1 dichloromethane–toluene mixture. This is in keeping with the recently reported femtosecond dynamics of dye M2 [35]. As a matter of fact.1 ps) to a non-emitting conformational intermediate. We conclude that the absorption and emission spectra of M2 in low-polarity solvents are due to essentially one and the same species. A close correspondence was observed between the absorption and excitation spectra. 3. . it ensues that M2.1 (chloroform) to 63. kem ¼ 660 nm) and emission (dotted line. the rather small Stokes shift and the mirror image relationship between the absorption and emission peaks suggest that fluorescence emission takes place from the local minimum of the initially excited 1 ðpH pà L Þ state. According to [35]. the excitation and monitoring wavelength. Representative spectra are shown in Fig. the fluorescence quantum yield should be very small. / Chemical Physics 288 (2003) 309–325 313 analysis of the solvatochromism of these dyes [34]. respectively. Thus. the absorption and fluorescence emission maxima of M2 were measured in nine solvents with ET ð30Þ ‘‘solvent polarity’’ parameter [25] ranging from 39. From the foregoing considerations. may be used to investigate solvatochromism in both absorption and emission. and some blurring of the vibronic structure possibly due to poor instrumental spectral resolution (8 nm). and the results are reported in Table 1. and shift quite regularly to the blue with increasing the value of ET ð30Þ which represents the overall solvation power of the solvents. In order to check the importance of any extra contribution to the absorption of M2 in solvents of low polarity. the static dielectric constant ðeÞ. 3) ca. Both absorption and emission spectra exhibit a negative solvatochromism.I. On the other hand. although emission is predicted to occur from the local minimum of the S1 ðpH pà L Þ state. Baraldi et al. 3.

470 17.460 0. Method and calculation details Incorporation of the solvaton model into the CS INDO method has already been described in detail [1.4 63.2]. / Chemical Physics 288 (2003) 309–325 Table 1 Absorption and emission maxima of M2 in solvents of different characteristics Solvent Chloroform Dichloromethane Acetone DMFe DMSOf Acetonitrile 2-Propanol Methanol Water Dmmax ðcmÀ1 Þ a b ET ð30Þa (kcal/mol) 39. c Dielectric constant at room temperature (20 or 25 °C) [13].7 55. d Typical uncertainties: Æ30 cmÀ1 on absorption. k ðeÞ is a solvent polarity factor related to the static dielectric constant e.590 18. According to this scheme.762 1.9 32.5 19.355 0. mmax ðcmÀ1 Þ 15.700 22.9 20. yet less pronounced.2 45. Æ60 cmÀ1 on emission. we only summarize the main points concerning the calculation of the solvatochromic shifts.310 16. O) and their charges were taken equal to the negative of the respective net p-electron charges. QB0 is the charge of the solvaton associated with atom B and cAB0 is taken equal to the electron repulsion integral cAB . mmax ðcmÀ1 Þ 16.7 42.130 16. We note that a qualitatively similar. ð 1Þ 0 Þ is the CS INDO matrix where the first term ðFlm element in the absence of solvent [3].4 Absorptiond .450 20.1 40. Briefly.314 I.7 37.8 8.190 )1340 0. In keeping with Costanciel and TapiaÕs virtual charge model the polarity factor pffiffi [9]. Dmflu max ¼ À1340 cm . f Dimethyl sulfoxide. where pffiffi is set equal to ð e À 1Þ= e.546 0.2]).820 16.6 50.386 0. Here.2 43.0 46.1 N ET b ec 4. fails to account for the quite different band shifts induced by aprotic and protic solvents of comparable polarity. the Fock matrix general element is expressed as s 0 Flm ¼ Flm À dlm k ðeÞ N X B0 QB0 cAB0 ðl 2 AÞ. Much smaller hypsochromic shifts were observed for À1 emission.7 37.390 17.120 17.260 16. e Dimethylformamide.160 16.850 15. As suggested by the experimental observations (Section 2. The determination of the solvent effects on the position of the first absorption bands required the Hartree–Fock equations incorporating solute– solvaton interactions to be resolved for the equilibrium ground-state geometries and the corresponding vertical S0 ! S1 ðpH pà L Þ transitions to be calculated at different values of k ðeÞ. non-specific solvent effects.309 0. while the second term accounts for the electron–solvaton interaction effects. solvent dependence of the absorption and fluorescence spectra has recently been reported for another negatively solvatochromic merocyanine (MC 540) [36].259 0.444 0.1.2) fluorescence emission of both M1 and M2 dyes takes place from the excited S1 ðpH pà L Þ state after geometrical relaxation of the solute and reorganization of the solvent molecules in the solvation shell. As pointed out in Section 1 (see also [1. we assumed k ðeÞ to range from 0 (when e is 1) to 1 (for e ! 1).040 17. N.1 45. The maximum solvatochromic shift found for the absorption.140 16.7 78. Dmabs max ¼ mðchloroformÞ À mðwaterÞ ¼ À6260 cmÀ1 . 3. solvatons were only associated with the atoms contributing to the p system (C. Baraldi et al. the fluorescence . and references cited therein).000 ‘‘Solvent polarity’’ parameter of Dimroth and Reichardt measured at 25 °C and 1 bar [25]. is in agreement with data of other authors ([25]. In particular. Theoretical investigation 3.150 17.570 )6260 Fluorescenced .700 17. N Normalized ET value.

entering the calculation of the core repulsion energy. Finally.e. The structural differences between the two dyes in the ground state and the geometry changes induced by the S0 ! S1 excitation can be illustrated by analysing the extent of bond length alternation (BLA) in the conjugated bridge connecting the donor (amino) and the acceptor (carbonyl) groups. 0 aCN ¼ 1:40. S1 ðpH pà L Þ. However.I. knr ¼ 0:72. The parameters peculiar to the CS INDO method [3] were chosen as follows: (i) the screening constants. in the present work geometrical distortions induced by the solvaton field on the solute molecule were disregarded. The geometry optimizations were carried out introducing in our CS INDO CI programs an optimization code where the gradient is calculated numerically within a Fletcher–Powell-type optimization algorithm [37]. we limited ourselves to standard S-CI calculations. optimized solvaton sets corresponding to the excited-state net p-electron charges and the MOs to be used in the CI calculation of the emission spectra and solvent-induced fluorescence shifts. Results and discussion 3.) and R0 AB (A). which reflects the relative . since solvatochromic shifts are mainly determined by polarization and electrostatic effects that are not very sensitive to small geometry modifications. For the sake of simplicity. / Chemical Physics 288 (2003) 309–325 315 transitions were calculated at different k ðeÞ values using geometries and solvaton charges optimized for the excited state. The so obtained geometries were used to generate.2. (ii)  the atomic pair parameters. i. knn ¼ 0:68. the solvaton charges suitable for the equilibrium excited state were simply derived from the net p-electron charges of the 1 UðpH pà L Þ configuration. were given the values: krr ¼ 1. This simplification appears to be acceptable. With these geometries. The optimized bond lengths are reported in Table 2. (ii) An analogous procedure was carried out to calculate fluorosolvatochromic shifts. using solvaton charges corresponding to the S0 net p-electron charges. SCF calculations were carried out. In view of the model character of this study. Baraldi et al. by performing a sequence of SCF (for S0 ) and SCF CI (for S1 ) calculations until convergence of the QB0 values. where the indexes refer to two hybrid atomic orbitals of the CS INDO basis set. two-electron repulsion integrals were calculated according to Ohno–Klopman [38]. The way the gradient is computed makes the program easily adaptable for calculations of excited-state geometries. R0 CC ¼ 1:7. of the benzene rings. 3. In other words. the equilibrium geometry of the S1 ðpH pà L Þ state of the isolated molecule was calculated by minimizing the excited-state energy ½EðS1 Þ ¼ EðS0 Þ þ DEðS0 À S1 ފ derived from the CI calculation as a function of the internal coordinates of the chromophoric group. thus determining the absorption spectral shifts. krp ¼ 0:65. we carried out the following set of calculations: (i) The S0 -state equilibrium geometries of both dyes were calculated by minimizing the total CS INDO SCF energy of the isolated molecule. aCO ¼ 1:20. we simply used geometries optimized in the absence of solvent ðk ðeÞ ¼ 0Þ. the CS INDO based approach described in the Section 3. kpp ¼ 0:50.1.u. Ground. Since the excited state responsible for both the absorption colour band and the fluorescence emission. at different k ðeÞ values. First. knp ¼ 0:60. aAB (a. for each molecule. for different k ðeÞ values. not reported here for conciseness [39]. the solvaton charges corresponding to the equilibrium geometries of the ground and the excited states were adjusted by an iterative procedure. To summarize. The MO active spaces included all p and pà molecular orbitals of the chromophoric groups and. RCO ¼ 2:10. as a function of the internal coordinates of the chromophoric group. The remaining pair parameters were given the usual values. aAB ¼ 1:50 and R0 AB ¼ 2:00.and excited-state equilibrium geometries After exhaustive test calculations on ground and excited state geometries of prototypic systems. is fully represented by the singly excited 1 UðpH pà L Þ configuration. The MOs produced at each k ðeÞ value by the iteratively adjusted solvaton set were then used for the CI calculation of the absorption spectrum.1 was applied to M1 and M2 in both S0 and S1 states.2. for M1.. klm . were assigned the values aCC ¼ 1:35.

. A vanishing BLA parameter. so high positive (negative) value of the BLA parameter indicates predominance of the neutral (zwitterionic) mesomeric structure.447 1.430 1. defined as the difference between the average length of the ‘‘single’’ bonds and that of the ‘‘double’’ bonds [16].215 A evident.44 A ). S1 ފ.055a 0.365 1. in this case BLA is already rather small in the ground state (0. 1).398 1. Neutral (quinonoid) and zwitterionic (benzenoid) forms of dye M2. such structure is at variance with the CS INDO optimized geometry of the isolated molecule (Table 2) which corresponds to a mixture of the two VB forms.346 ) connected to the six-membered rings by bonds A . 4.008c 0.444 1.396 1. However.398 1. 2. S0 Þ > BLA ðM2. However. on the other hand. the contribution of the neutral VB structure becomes lower on moving from S0 to S1 ½BLA ðM1. The ‘‘single’’ and ‘‘double’’ bonds were identified by reference to the neutral VB structures (see Fig. The differences between the two dyes become more evident if the BLA parameters of M2 are calculated in terms of the bonds (d.430 1. d. As is longer than a double C@O bond (1. e.402 1. BLA ðM1Þ ¼ ðc þ e À b À dÞ=2. as far as we know. b BLA ðM2Þ ¼ ðc þ e þ g þ i À b À d À f À hÞ=4.024b )0.374 1. 2).304 A ) rather of $1. c BLA ðM2Þ ¼ e À ðd þ f Þ=2. 4).411 1. Baraldi et al.027a For labelling of the bonds. .368 1. f C–C bonds).419 1.017c S1 1.19] in that all calculations predict the quinonoid form to be (more or less) prevailing in the isolated molecule.418 1. see Fig.401 1. with a slight prevalence of the neutral (quinonoid) one (Fig.245 S1 1.415 1. The CS INDO optimized geometry of M2 is in qualitative agreement with previous theoretical studies [10.450 1.458 1. the crystal structure is assimilable to that of M2 in aqueous solution.253 M2 S0 1. thus reflecting an opposite bond alternation with respect to S0 .455 1.436 1.362 1. indicates a cyanine-like structure characterized by similar weights of the two forms.316 I.450 1. / Chemical Physics 288 (2003) 309–325 Table 2 Bond lengths and bond length alternation (BLA) parameters for the ground state ðS0 Þ and the first ppà excited state ðS1 Þ of dyes M1 and M2 Bonds M1 S0 a b c d e f g h i l BLA 1. a weights of the neutral polyenic and zwitterionic structures in the VB resonance hybrid (Fig.406 1. the calculation results of Table 2 indicate that: (i) in the ground state. with reference to the central polymethine fragment (e.447 1. S0 ފ. Thus. All such characteristics are well expressed by the value of the so called BLA parameter (last row of Table 2). S0 Þ > BLA ðM1.421 1.427 1. structure determinations and calculations have been reported only for dye M2.e. BLA ðM2. This is not surprising since in the crystal the zwitterionic form is imposed by the formation of hydrogen bonds between the carbonyl end of the chromophore and the crystal water. S0 Þ > BLA ðM2.038b 0.446 1. the chargeseparated form is more important for M2 than for M1 ½BLA ðM1. On this basis. From the crystal structure determination of M2 trihydrate [40] the molecule was found to be almost planar and to have a zwitterionic (benzenoid) structure with an essentially double C–C central bond (1. and a C–O bond (1.250 0.254 0. The goodness of our theoretical predictions should now be verified by comparing the calculated ground-state geometries of Table 2 with the experimentally determined structures as well as the results of previous theoretical studies. As a matter of fact. our geometry exhibits the smallest BLA Fig. (ii) in both merocyanines bond-length alternation decreases upon electronic excitation. S1 Þ.14. i. f) of the central polymethinic fragment.447 1.16.017) and changes sign in S1 .

077). is associated to charge transfer along the longitudinal molecular axis. Such growing is little higher when using the equilibrium geometry of the excited state (Table 4). n ¼ 2. while the contrary occurs for oscillator strength and solvent shift of the S0 ! S1 transition (see [2]). both the absorption and fluorescence maxima of M1 are predicted to undergo marked bathochromic shifts (DmðS0 ! S1 Þ ¼ þ3550 cmÀ1 and DmðS1 ! S0 Þ ¼ þ 5000 cmÀ1 ) 4.. together with the oscillator strengths of the transitions (f).9) by the CS INDO CI procedure described in Section 3. while the S0 –S1 transition is polarized perpendicularly to the twofold axis ð1 BÞ. The results ðDEÞ are collected in Tables 3–6. 1. while the oscillator strengths are found to be both quite high (>2) and not very sensitive to solvent polarity. which increases with increasing solvent polarity.058. the electric dipole moments (l).13. [14]: 0. / Chemical Physics 288 (2003) 309–325 317 value (present work: 0. [16]: 0. but Dl ¼ lS1 À lS0 is predicted to 4 Dm ¼ mðnon-polar solventÞ À mðpolar solventÞ.1. be almost the same in absorption (Table 3) and emission (Table 4) at all values of k ðeÞ. Thus.9. [19]: 0. and the net charges on the nitrogen and oxygen atoms in the S0 ðQN. A more correct correlation between the solvatochromic behaviour of ketocyanine M1 and that of its parent chromophore emerges by changing from the dipole moments (i. R ¼ Me) and its N-phenyl derivative in the absence of solvent. corroborate the theoretical prediction even if transition energies and spectral shift are a little overestimated because of the adopted simplifications (essentially..017. the S0 and S1 dipole moments of the ketocyanine M1 (and their increase with increasing k ðeÞ) turn out to be decidedly smaller than those of its pentamethine–merocyanine moiety. i. in S0 an increase of k ðeÞ results in a drift of electrons from the two nitrogen atoms (donors) to the . but we can say that this result is consistent with the observed solvatochromic behaviour of M2. However. also reported in Table 7. resulting in a solvent-induced stabilization of the excited state relative to the ground state. The bathochromic shifts are related to the increase of the solute dipole moment on the S0 ! S1 transition.e. 2).2] where both permanent and transition dipole moments are aligned with the chromophoric chain. We do not deny that our calculation may have underestimated the contribution of the quinonoid form. closely resemble those previously found for streptopentamethine–merocyanine [2].18]. First of all. singly excited CI and coplanarity of the phenyl ring). Absorption and fluorescence solvatochromism Using the S0 and S1 optimized geometries. we carried out CS INDO SCI test calculations for pentamethine–merocyanine (Fig.. let us point out some essential characteristics of the theoretical description. an initial small red shift followed by a large blue shift of the first absorption band on going from low polar to highly polar solvents [1. The polarization effects induced by the solvaton field on the electronic structure of the solute result in a quite regular growing of both lS0 and lS1 on going from k ðeÞ ¼ 0 to 0. In other words.O Þ and S1 ðQÃ N. i.2. Baraldi et al. In particular.2. The absorption data in dichloromethane. global electrical properties) to the atomic net charges reflecting the local charge distributions. The calculation results (Table 7) indicate that the phenyl substitution produces a small red shift and intensity increase of the transition.038. as well as their changes due to an increase of k ðeÞ and/or S0 ! S1 excitation. first row). while the other theoretical predictions favour more decidedly the quinonoid structure.2. it is worth noting that the permanent dipole moment of M1 is directed along the twofold axis containing the C@O bond (see Fig.I. while lS0 and lS1 remain almost unchanged and substantially higher than those of the ketocyanine (Table 3. As a matter of fact. As a matter of fact. 3.030. [10]: 0. For a more precise comparison.O Þ states. the dipolemoment change occurring on the S0 –S1 transition is not as effective a parameter of the solvatochromic effect as in the case of the parent streptopentamethine–merocyanine [1. our description reflects a resonance hybrid with similar weights of the two limiting structures. the vertical S0 ðeq:Þ ! S1 and S1 ðeq:Þ ! S0 transition energies of M1 and M2 were calculated in a medium of changing polarity (k ðeÞ ¼ 0–0. Table 3 shows that the net charges on the nitrogen and oxygen atoms in the ground state. Tables 3 and 4 show that on going from k ðeÞ ¼ 0 (gas phase) to k ðeÞ ¼ 0:9 (highly polar medium).e.e.

81 )0.86 lS1 (D) 8.558 2.22 +0.84 )0.686 2.56 19.425 1.30 11.126 2.99 9.10 )0.12 QO )0.9 DE (eV) 2.818 f 2.16 Qà O )0.6 0.91 43.0 0.04 0.74 )0.968 2.35 +0.28 QO )0.77 )0.09 26.16 Qà N +0.54 41.67 6.04 +0.884 1.47 Qà O )0.258 3.78 )0.01 +0.37 21.05 +0.91 32. lS1 Þ and net charges on nitrogen ðQN .2 0.2 0.47 10.04 +0.81 )0.4 0. ground and excited-state dipole moments ðlS0 . Baraldi et al.2 0.09 +0.80 39.498 f 2.07 +0.378 2.060 2.55 7.823 2.02 +0.345 2.21 +0.65 9.362 2.384 2.30 24.331 2.03 )1.81 10.163 3.367 2.702 1.92 )1.763 f 2.03 8.944 3.353 2.184 3.83 )0.757 1.00 )1.11 )1.98 )1.98 28.53 lS1 (D) 17.89 )1.27 26.36 21.15 Qà N +0.11 )1.37 +0.725 2.750 2.03 +0.12 lS1 (D) 18.6 0.6 0.21 Qà O )0.53 8.70 )0.86 8.732 2.06 )0.91 )0. osà cillator strength (f).952 2.05 +0.01 +0.09 )1.02 )1.86 )0.79 24.163 lS0 (D) 17.02 +0.08 +0.263 2.91 )1.0 0.05 +0.56 30.78 QN )0.0 0.782 2.223 lS0 ðDÞ 5.44 7.27 9.49 27.10 Table 5 Calculated S0 ! S1 absorption properties of M2 as functions of the solvent polarity factor k ðeÞ (see caption of Table 3 for the meaning of symbols) k ðeÞ 0.321 2.8 0.9 DE (eV) 3.83 )0.01 )1.13 )1.07 QO )0. QO Þ atoms k ðeÞ 0. / Chemical Physics 288 (2003) 309–325 Table 3 Calculated S0 ! S1 absorption properties of M1 as functions of the solvent polarity factor k ðeÞ: vertical transition energy ðDEÞ.03 0.04 )1.58 37.234 1.92 22.73 30.118 2.291 f 2.33 QN )0.71 )0.88 33.00 +0.732 2.007 1.81 QN )0.855 2.411 2.8 0.9 DE (eV) 3.87 )0.15 +0.72 )0. Qà N Þ and oxygen ðQO .79 )0.8 0.01 )1.16 +0.12 )0.9 DE (eV) 2.6 0.05 +0.10 +0.59 6.10 )1.23 +0.02 +0.10 8.16 +0.07 )1.08 Qà N )0.15 Table 6 Calculated S1 ! S0 emission properties of M2 as functions of the solvent polarity factor k ðeÞ (see caption of Table 3 for the meaning of symbols) k ðeÞ 0.94 )1.23 +0.95 )1.4 0.87 10.67 24.326 lS0 (D) 5.01 +0.14 +0.227 2.58 11.05 )1.4 0.13 Qà N )0.00 +0.09 )1.08 )0.2 0.45 QO )0.075 1.28 Qà O )0.318 I.14 Table 4 Calculated S1 ! S0 emission properties of M1 as functions of the solvent polarity factor k ðeÞ (see caption of Table 3 for the meaning of symbols) k ðeÞ 0.73 )0.73 )0.17 7.94 )1.02 )1.904 1.8 0.13 .4 0.11 6.10 7.0 0.699 lS0 (D) 19.91 )1.724 2.11 +0.790 2.01 +0.51 21.64 QN )0.13 )0.64 7.79 lS1 ðDÞ 8.10 +0.766 2.09 +0.

087 3. the Franck–Condon S1 state is 2–3 D less dipolar than S0 . Table 5 shows. in particular. oxygen atom (acceptor). traceable to an increased weight of the two equivalent zwitterionic forms the absorption maximum of M2 with increasing k ðeÞ. Table 4 shows that. Thus.797 1.43 13. lS1 is slightly higher than lS0 but.2. At k ðeÞ ¼ 0. Merocyanine M2 is predicted to have a very different solvatochromic behaviour both in absorption and in emission (Tables 5 and 6). inverting the direction of the charge transfer. similar considerations apply to the transition from the relaxed excited state to the Franck–Condon ground state.17 3. The latter phenomenon. both the small red shift between k ðeÞ ¼ 0 and 0. The blue-shift of the oscillator strength attributable to the increasing importance of the zwitterionic form (Fig. This behaviour follows that found in our previous theoretical study [1.25].2]. is accompanied by a substantial decrease of – giving rise to a nonamethine–cyanine-like electronic structure – relative to the neutral form (M1 in Fig. while the vertical S0 ! S1 transition results in a reduction of such electron-charge accumulation. and the successive strong blue shift can be rationalized in terms of net stabilization of S1 or S0 induced simply by dipolar solute–solvent interactions.55) and the use of fixed geometries optimized at k ðeÞ ¼ 0. Similar considerations can be made by analysing the net atomic charges. where permanent and transition dipole moments are both ‘‘parallel’’ to the longitudinal molecular axis. Q provides an estimate of the real N O O charge transfer occurring during the S0 ! S1 transition at each k ðeÞ. due to a substantial contribution of the zwitterionic VB structure. and grows rapidly with increasing k ðeÞ owing to growing solvent-induced polarization. the ketocyanine M1 provides an example of a system where the solvatochromic effects may be described within the solvaton model better than by using SCRF models adopting the Onsager dipolar approximation [16]. / Chemical Physics 288 (2003) 309–325 319 Table 7 Calculated and experimental properties of the S0 ! S1 transition of the streptopentamethine–merocyanine and its N-phenyl derivative Molecule Calculateda DE (eV) Me2 N½CH@CHŠ2 CHO PhNMe½CH@CHŠ2 CHOc a b f lS0 (D) lS1 (D) Experimentalb DE (eV) 10À3 emax 4. that in both S0 and S1 an increase in solvent polarity gives rise to an increase in electron population on the oxygen atom. from k ðeÞ ¼ 0:2 on.9. the absorption maximum is found to undergo a small bathochromic shift (until k ðeÞ ¼ 0:2) followed by a large hypsochromic shift leading to a global strongly negative solvatochromism ðDm ffi À4100 cmÀ1 Þ (Table 5). 1). the comparison between Qà N. [41].64 8. Briefly. In dichloromethane. In this case. which is the opposite of that found with M1 (see Table 3). even if the transition energies and the solvatochromic shift turn out to be somewhat reduced because of some differences in the calculation procedure concerning the parametrization (kpp ¼ 0:5 instead of 0. as expected for a polar solute in a polar solvent [20.211 1. Table 5 shows that lS0 is quite high at k ðeÞ ¼ 0. S1 ðeq:Þ ! S0 .I. suggests that S0 ! S1 excitation produces an enrichment of the resonance hybrid in the quinonoid form.430 3. c The phenyl ring was assumed to be coplanar with the chomophore chain and to have the benzene structure. Baraldi et al. In going from k ðeÞ ¼ 0 to 0. In conclusion.360 8. 4). The same set of calculations performed for .337 51 65 At k ðeÞ ¼ 0. Qà and Q . Moreover. the S0 and S1 dipole moments should be fully representative of the solvatochromic behaviour.49 13.

320 I. Wavenumber of the calculated and experimental absorption maximum of M1 vs. we have plotted in a same diagram the calculated and experimental band frequencies (in cmÀ1 ) using. and keeps almost constant over the entire range of solN vent polarity ($0. In order to make such comparison as concise and comprehensive as possible.5 eV at k ðeÞ. Let us comment first on Figs. the calculated Dmmax values ½mðk ¼ 0Þ À mðk ¼ 0:9ފ for absorption ðþ3550 cmÀ1 Þ and emission ðþ5000 cmÀ1 Þ are in good qualitative agreement with the experimental Fig. these results have to be compared with the observed solvato. the N k ðeÞ and ET [25] scales. derived by simple linear interpolations. As a matter of fact. THF. Two points.. As a consequence. both ranging from 0. the solvatochromic shifts. ones ½mðET À1 þ3980 cm . The experimental mmax values are reported from [26. Dmfluo ffi þ4350 .0. As is evident. 5) and emission (Fig. apart from the systematic blue-shift of the calculated S0 ðeq:Þ ! S1 and S1 ðeq:Þ ! S0 transitions (essentially due to the adopted CI truncation).9) of solvent-polarity parameter. DMF. Baraldi et al.090 to 1. ethanol.and fluorosolvatochromic behaviours of M1 and M2. [27]: þ3600.45 N eV at k ðeÞ. 6). is related to the fact that the solvaton field acting on the equilibrium excited state is weak compared with that acting on the equilibrium ground state. N N ¼ 0:1Þ À mðET ¼ 1:0ފ ([26]: þ4010. have to be noted: (i) lS1 À lS0 is negative over the whole range of k ðeÞ. the agreement becomes even better if the comparison is made over the same interval (0. / Chemical Physics 288 (2003) 309–325 the vertical S1 ðeq:Þ ! S0 transition. respectively. were found to be: Dmabs =cmÀ1 ffi þ3170 ðcalcd:Þ.e. þ3260 [26]. methanol and water) with ET ranging from 0. In this case. which is contrary to that exhibited by M1 (Tables 3 and 4) (where lS1 > lS0 ). The above discussion has shown how the adopted theoretical scheme is reflected in the calculation results. ET ¼ 0:9). Thus. However. 5. the deviation is nearly the same for absorption (Fig. 7 and 8). respectively. led to similar trends of the dipole moments and net charges (Table 6). 5 for the solvent characteristics). are reported from [26. 5 and 6. the calculated mmax values are overestimated with respect to the experimental values. Now. The experimental mmax values in eight solvents (toluene. the k ðeÞ and normalized N ET values of solvent polarity. however. Wavenumber of the calculated and experimental emission maximum of M1 vs. with a global negative solvatochromism of just À250 cmÀ1 ()0. i. 6. our simple solvaton–CS INDO scheme describes fairly well the absorption and fluorescence properties of ketocyanine M1 as well as their dependence on the solvent characteristics.27] (see caption of Fig. (ii) the increase of lS1 and lS0 with increasing k ðeÞ is less marked than that found for the vertical S0 ðeq:Þ ! S1 transition (Table 5). respectively.000.0 to 1. ET ¼ 0:1 and $0. þ3880 cmÀ1 ). the k ðeÞ and norN malized ET values of solvent polarity. Fig. acetone. 2-proN panol. This way. the S1 ðeq:Þ ! S0 transition energy turns out to be little affected by solvent polarity. Such trend. 5 and 6) and M2 (Figs.1–0. we obtained four diagrams corresponding to the absorption and fluorescence properties of M1 (Figs.27]. using geometry and solvaton charges of the relaxed excited state. þ2800 [27]. Interestingly.031 eV) (Table 6).

Now.and fluorosolvatochromic shifts seem to be to a great extent determined by non-specifc solute–solvent interactions. while the experimental ones first bend and then undergo a dramatic drop down N in water (ET ¼ 1:0). at k ðeÞ ¼ 0 the calculated red shifts are 0. 8. the k ðeÞ and ET values of solvent polarity.5 eV. 7 and 8). Wavenumber of the calculated and experimental emission maximum of M2 vs. 7. 5 and 6). Baraldi et al. 5 for the solvent characteristics). In spite of the large fluctuations of the experimental data.38 eV. the remaining experimental points Fig. leaving out solvents N with ET > 0:7. the theoretical plot goes on increasing. Fig. Calculated and experimental Stokes shift of M1 vs. Such estimates N indicate that excepting solvents with very high ET . In low polarity solvents. the k ðeÞ and normalized N ET values of solvent polarity. The same thing emerges from the fluo plots of the Stokes shifts (mabs max À mmax ¼ DmðabsÀ fluoÞ) vs the normalized solvent-polarity parameters (Fig. see Tables 3 and 5 and Tables 4 and 6) even if the individual transition energies are rather overestimated ($0. / Chemical Physics 288 (2003) 309–325 321 Fig. reN values of solvent pospectively. þ3810 [26]. in M1 the fluorescence is more sensitive than the absorption to solvent polarity. 9. .27] (see caption of Fig. N ET ¼ 0:3) due to the adopted CI limitations. This behaviour.7 eV at k ðeÞ. originating in the marked ‘‘orientational’’ stabilization of the emitting state S1 [20] is evidenced by the fact that. þ3710 [27].48 and 0. The mmax covering the entire range of ET values of Table 1 are also reported. the k ðeÞ and normalized ET larity. Wavenumber of the calculated and experimental abN sorption maximum of M2 vs. respectively. Experimental values were derived from [26. it is evident that calculated and observed Stokes shifts of M1 exhibit similar plots N until ET ffi 0:7 . The experimental data in 25 solvents N were taken from [18]. This is correctly predicted by calculations (e.I. let us consider the stilbazolium betaine M2 (Figs. The experimental mmax values are those of Table 1. where specific solute–solvent interactions become very important. (ii) except for ET P 0:7. the absorption and emission maxima of M2 are redshifted with respect to those of M1 of more or less 0. in M1 solvato. are aligned almost parallely to the theoretical plots (Figs. respectively. 7 shows that both the initial small red shift and the Fig.. respectively. 9). Beyond this value. any discussion considering only the overall spectral shifts between water N N (ET ¼ 1:0) and toluene (ET ffi 0:1) may lead to N wrong interpretations.g. ðcalcd:Þ. We can conclude that: (i) due to the water peculiarity.

10. contrary to what occurs in the case of M1 ðlS1 > lS0 Þ. The reason for this somewhat surprising result lies in the way the solute–solvaton interactions were included in the molecular HamFig. the different relative weights of the neutral and zwitterionic VB structures) and of their evolution with increasing the solvent polarity. contrary to what is found for M1 (Fig. Figs. This is fully confirmed by our fluorescence study on M2 in various solfluo À1 vents showing that mfluo chloroform À mwater ¼ À1340 cm (Table 1 and Fig. the large negative solvaabs tochromism of M2 (mabs chloroform À mwater ¼ À6260 À1 À1 cm (Table 1). This is likely due to the fact that the probe used to develop this scale (pyridinium N-phenolate betaine) [25] is chemically more similar to M2 than to M1. about a fifth of the blueshift observed in absorption. This occurs for opposite reasons in the two dyes: in M1 the Stokes shift raises because the bathochromic shift of the fluorescence is greater than that of the absorption. 9). k ðeÞ¼0:9 In other words. in this case ðlS1 < lS0 Þ fluorosolvatochromism should be expected to be weaker than solvatochromism. in both systems the Stokes shift increases considerably (with the only exception of M1 in water) with increasing the solvation N power of the solvent (as expressed by the ET value). On the contrary (Fig.. Moreover. Calculations underestimate fluorosolvatochromic effects to the same extent as the solvatochromic ones. but in both cases the effects are predicted to be weaker than the experimental ones. 10 shows that the solvation power of hydrogen-bond donor solvents towards M2 (in both the ground and the excited N states) is well described by the ET ð30Þ ðET Þ parameter. see Table 5 and Fig. the solvation power of such solvents (primarily water) towards M1 is poorly described within the N ET ð30Þ ðET ) solvent scale. the calculation results agree with experiment as regards the direction of the spectral shifts of absorption and fluorescence maxima.36]. the k ðeÞ and normalized ET larity. i.e. Calculated and experimental Stokes shift of M2 vs. actually accounts fairly well for the effects of media characterized by N quite high ET values where specific (H-bond) interactions are expected to be as important as dipolar interactions. As is evident. as clearly shown by Fig. in M2 the same phenomenon is due to the hypsochromic shift of the absorption being greater than that of the fluorescence. / Chemical Physics 288 (2003) 309–325 successive strong blue shift of the absorption band N of M2 observed on increasing the ET value are qualitatively well reproduced by the calculations. Although dyes M1 and M2 exhibit opposite solvatochromic and fluorosolvatochromic behaviours..e. 9 and 10 lend themselves to the following concluding remarks. and indicate that the Stokes range of ET shift of M2 increases rapidly on increasing the solvent polarity. .322 I. The experimental values derive from the absorption and emission data of Table 1. so mfluo k ðeÞ¼0:2 À À1 mfluo reduces to $ À 300 cm (Table 6. 8). it should be noted (see also Figs. Interestingly. the theoretical and experi- mental plots of Dmðabs À fluoÞ are in very good agreement over the experimentally investigated N values. in this case the experimental plot displays no inversion 5 and remains parallel to N the theoretical one until ET ¼ 1:0. This allows for a much better agreement between calculated and observed Stokes shifts (Dmðabs À fluoÞ). formally including only electrostatic solute–solvent interactions. Fig. 8). A better general description could be achieved with proper multiparameter approaches [25. 10. 9). According to the previous discussion on the values and solvent-induced changes of dipole moments. À6490 cm [18. Both phenomena are well described within the solvaton–CS INDO scheme and can be rationalized in terms of the different freemolecule electronic structures (i. but such correlation analysis does not fall within the purposes of this work. on the contrary. 5–8) that the solvaton–CS INDO approach. N values of solvent porespectively.25]) is somewhat underestimated by the solvaton–CS INDO calcuabs À1 lations (mabs k ðeÞ¼0:2 À mk ðeÞ¼0:9 ffi À4230 cm . Baraldi et al. 7). Quantitatively speaking. 5 Fig.

[27] evaluated the ratio lS1 =lS0 to be equal to 1.. In order to carry out an exhaustive test. to our knowledge. we chose the ketocyanine M1 which has been the subject of extensive experimental work. The use of solvaton sets reflecting the net p-electron charges proved to be most effective to rule the evolution of the resonance hybrid composition of S0 and S1 as the solvent polarity increases. using the solvatochromic comparison method. the molecular geometries in the equilibrium S0 and S1 states were approximated by those optimized in the absence of solvent. Since. (1)). as it happens in the case of the strongly fluorescent M1. / Chemical Physics 288 (2003) 309–325 323 iltonian. The stilbazolium betaine M2 was chosen for the large negative solvatochromism of its absorption band.g. lS1 =lS0 ¼ 1:44).I.. the theoretical descriptions of solvatochromism and fluorosolvatochromism were undertaken within the same conventional scheme. we searched for two sample merocyanines characterized by opposite solvent effects.1. The solvent-dependent composition of the resonance hybrid between the covalent and the zwitterionic VB structures was taken as the key to interpret the calculated ground and excited-state properties of the two merocyanines at the various k ðeÞ values. Baraldi et al. our procedure acts prevalently on the p-electron system by correction terms linearly related to the solvation parameter k ðeÞ (Eq. Moreover. As reminded in Sections 1 and 3. setup using the subset of the net p-electron charges. This interpretation is plausible since it has been shown [19] that the effects of protic solvents on merocyanine spectra may be described within p-electron theory using heteroatom parameters corresponding to the molecule protonated on the oxygen. The equilibrium absorbing and emitting units (molecule + solvaton pattern) and the corresponding S0 ! S1 and S1 ! S0 vertical transitions were studied for M1 and M2 as a function of a polarity factor formally related to the dielectric pffiffi p ffiffi constant. However. According to this body of experimental evidence. the emission properties of M2 had never been reported before. which has been widely studied both experimentally and theoretically. i. On moving from S0 to S1 . Such a scheme was directly applied within the solvaton–CS INDO method. it results in opposite solvatochromic behaviours in both absorption and emission. k ðeÞ ¼ ð e À 1Þ= e. Introduction of a polar solvent stabilizes the zwitterionic forms but. Banerjee et al. calculating the shifts induced by a solvent-polarity change on the vertical S0 ðeq:Þ ! S1 ðFranck–CondonÞ and S1 ðeq:Þ ! S0 ðFranck–CondonÞ transitions. For the sake of simplicity. the analysis of the fluorescence emission and excitation spectra led us to conclude that. even if the phenomenon is less marked in M2 than in M1. Table 5 shows that for M1 the theoretical prediction is in very good agreement with experiment (at k ðeÞ ¼ 0. the emission of M2 originates from the local minimum of the solvated S1 ðpH pà L Þ state. and the respective solvaton patterns. the contribution of the charge-separated structure increases in both dyes. A complete validation of the calculated ground and excited-state dipole moments was not possible for lack of experimental data. due to the difference in the starting electronic structures. We found that M2 is rather weakly fluorescent and exhibits negative fluorosolvatochromism. the modifications of the Fpp elements at high k ðeÞ values may well account for the effects of H-bond interactions occurring in the molecular plane (e. 4. The analysis of the gas-phase optimized geometries in terms of BLA parameter showed that in the ground state M1 has a markedly covalent character while in M2 the covalent character is nearly balanced by the zwitterionic one. those involving the sp2 -like oxygen lone pairs).4 for dye M1. were adjusted iteratively starting from those corresponding to the unsolvated molecules. The description of the solute–solvent interaction in terms of local charge distributions . even if the emission is much less sensitive to a change of solvent polarity than the absorption. Summary and conclusions The main purpose of the present paper was to appraise the capability of the solvaton–CS INDO model to arrange both solvatochromism and fluorosolvatochromism of merocyanine dyes. Within this s scheme. we carried out an experimental investigation on the matter.e. As a prototypic dye exhibiting large positive solvatochromism on both absorption and emission.

Struct. [11] A. To sum up. I. Lett. Reichardt. Vanossi. II (1995) 483.C. Acta 34 (1974) 145. Phys. Acta 35 (1974) 273.7 eV) of the transition energies the solvaton–CS INDO calculations provided good descriptions of the opposite solvatochromic behaviours of M1 and M2 in both absorption and emission. A thorough comparison with the experimental data was made possible by the construction of diagrams where calculated and observed frequencies of the absorption and emission maxima were N plotted against the k ðeÞ and ET solvent polarity parameters. Academic Press. Lett. C. this being at variance with all solvaton models (e. Baraldi. Soc. Corre. II 80 (1984) 1235. da Silva.P. Chem. B. (Theochem) 304 (1994) 191. Quantitatively speaking. Machado. O. J. [15] L. Mol. 65 (1979) 395. Momicchioli. Miertus. 238 (1998) 353. Phys. P. Germer. Phys. A. Vanossi. Phys. D. [12] J. Miertus. 194 (1995) 101. Thus. O. at least as far as the main qualitative aspects are concerned (but also the sizes of the solvent shifts were in general well reproduced). O. We are indebted to Dr. Chem. Soc. Phys. G. J. Costanciel. References [1] I. Tapia. / Chemical Physics 288 (2003) 309–325 makes the solvaton model free from symmetry imposed restraints. both ranging from 0 to 1. [4] G. [14] J.5–0. On the contrary. [9] R. [2] I. Le Beuze. except for the peculiar behaviour of M1 in water. Quite surprisingly. the solvaton model provides fully consistent descriptions for the M1 and M2 solvatochromisms. 1979. [10] A. Chem. Solvent Effects in Organic Chemistry. Theor. Ponterini. H. Kysel. F. Ponterini. Adv. Chim. the solvent shifts of the absorption and fluorescence spectra were correlated better for the positively solvatochromic ketocyanine than for the negatively solvatochromic stilbazolium betaine. Germer. London. 82 (1983) 229. Morley. M. J. [8] S. SCRF) where the solute is treated as a point dipole. the controversy that arose some years ago in the interpretation of the solvatochromism of M2 (see Section 1) came from theoretical treatments devoid of this prerequisite. G. Baraldi. Botrel.C. Baraldi.g. Chem. Acta 48 (1978) 383. [13] C.A. We notice that. Perkin Trans. This happens since the polarization of the p-electron system induced by specific (H-bond) solvent interactions taking place in the molecular plane is implicitly accounted for within our formulation of the solvaton model. Flament for providing us with his geometry optimization program and to Prof. Chim. Chem. G. in very good agreement with experiment the Stokes shifts (Dmðabs À fluoÞ) of both M1 and M2 were predicted to substantially increase (especially in the case of M2) on increasing the solvent polarity.324 I. the solvaton–CS INDO method was applied to the study of solvent effects on both absorption and fluorescence spectra of positively and negatively solvatochromic merocyanines. [6] H. [5] H. Klopman. where the solvatochromic ranges (mðnon-polar solventÞ À mðhighly polar solventÞ) of absorption and emission were both somewhat underestimated. Chem. Acknowledgements This research was jointly supported by the MURST (Roma) and the University of Modena and Reggio Emilia within the ‘‘Programmi di Ricerca di Interesse Nazionale’’.. Chim. Berthier for valuable discussions. Faraday Trans. Kysel. Chem. 36 (1999) 121. Colour and Constitution of Organic Molecules. However. Momicchioli.O. Griffiths. Baraldi et al. 21 (1977) 27. An elementary condition underlying these results is that the electronic transitions of the solute were generated in the presence of the polarized solvent. J. Such a severe test has been passed rather well. Theor. Chem. Jacques. Bruni. F. D. Rezende. 1976. [7] S. F. Tonnard. M. Theor. Apart from a systematic overestimation (0. Quantum Chem. Straub. [3] F. 1 (1967) 200.A. Aboad. Weinheim. F. the solvaton–CS INDO model is capable of accounting for the solvation effects on merocyanine spectra over almost the N entire range of the normalized ET values. Botrel. Verlag Chemie. Phys. the fact that M1 has moderate S0 and S1 dipole moments perpendicular to the conjugated chain (the longitudinal components being equal to zero by symmetry) while M2 has large dipole moments aligned with the long molecular axis leads to quite different reaction fields (and solute–solvent interaction energies) within the dipolar approximation in spite of the basic similarities of the two systems. Momicchioli. .

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