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CHAPTER

FOUR Estimation of the First Hyperpolarizability of a Series of p-Nitroaniline Derivatives

4.1

Introduction

The electro-optic effect can be brought about in a polymer matrix by the addition of non-centrosymmetric dipolar molecules. These molecules possess high second order susceptibilities and are sometimes called nonlinear optical chromophores.1 The molecular second order susceptibility is also termed as the first hyperpolarizability βijk , where i, j and k refers to molecular axes. The synthesis and study of molecules with large first order hyperpolarizabilities is important due to the potential applications of such molecules in nonlinear optics. Many components for optical signal processing and communication devices can be made out of materials possessing high electrooptic coefficients.2 This chapter gives the details of the molecules studied for nonlinear optical properties. The molecular parameters including ground state dipole moment, excited state dipole moment and the first hyperpolarizability were estimated. The aim was to make a selection of molecules with comparatively higher values for the figure of merit explained in Section 1.5.3. The estimation of the first hyperpolarizability was done using the two level microscopic model of βijk . The techniques available to measure this

N-bis(4-[(n-aminoalkyl)amino]butyl)-4-nitrobenzenamine. 8 The structure of the molecules studied are given in Fig.2 Molecules studied All molecules were synthesized in our lab and the details are given elsewhere.2 and 4. 4. The main difference between the molecules was in the number of alkyl spacers connecting the acceptor group and the donor group. 2b.7.96 Molecules studied important parameter are second harmonic generation.1: N. 2d and 2e.6 This method requires the excited state dipole moment. Br N Br NO2 Figure 4. .5 An estimation of first hyperpolarizability can be done using the simplified two level model also.2: N. 4.3 electric field induced second harmonic generation (EFISH)4 and hyper-Raleigh scattering. H2N n NH N NH NH2 n n = 2-6 NO 2 Figure 4.N-bis(4-bromobutyl)-4-nitrobenzenamine (1a).1. Solvatochromism involves studying the effect of solvent polarity on the molecule’s absorption and fluorescence spectra. 2c. 4.3. which can be estimated using solvatochromism and the ground state dipole moment which can be estimated using the Debye-Guggenheim method. Molecules with this general structure were labeled as 2a.

1 shows the labeling of the molecules adopted during the experiments.N-bis(4-[(2-aminoethyl)amino]butyl)-4-nitrobenzenamine N.N-bis(4-[(3-aminopropyl)amino]butyl)-4-nitrobenzenamine N. correspondingly there were a total of 10 molecules under study.Molecules studied H3C NH NH n NH N NH n CH3 97 n = 2-6 NO2 Figure 4. In the second set.1: Details of the molecules n IUPAC Name N.N-bis(4-[(6-aminohexyl)amino]butyl)-4-nitrobenzenamine N. 1a 2a 2b 2c 2d 2e 3a 3b 3c 3d 2 3 4 5 6 2 3 4 6 N.N-bis(4-bromobutyl)-4-nitrobenzenamine No. 3b. n = 5 was not available for studies. Table 4. The number of alkyl units was varied from n = 2 to 6.N-bis(4-[2-(ethylamino)ethylamino]butyl)-4-nitrobenzenamine N.N-bis(4-[4-(ethylamino)butylamino]butyl)-4-nitrobenzenamine N.N-bis(4-[(5-aminopentyl)amino]butyl)-4-nitrobenzenamine N. Table 4.N-bis(4-[(4-aminobutyl)amino]butyl)-4-nitrobenzenamine N.3: N. Molecules with this general structure were labeled as 3a.N-bis(4-[3-(ethylamino)propylamino]butyl)-4-nitrobenzenamine N. 3c and 3d. N-bis(4-[n-(ethyl amino)alkyl amino]butyl)-4nitrobenzenamine.N-bis(4-[6-(ethylamino)hexylamino]butyl)-4-nitrobenzenamine .

several concentrations of the molecules under investigation were prepared in toluene (being a non-polar solvent) and filled between the plates of a parallel plate capacitor with variable plate separation and the capacitance was measured as a function of plate separation . n0 and ρ0 are the dielectric constant. Thus an idea about the magnitude of this molecular property is useful when deciding the poling requirements to induce non-centrosymmetry.3 Determination of ground state dipole moment (µg ) The figure of merit of nonlinear optical chromophores is highly dependent on the ground state dipole moment and the first hyperpolarizability of the molecule. refractive index and the density of pure solvent respectively. the tendency of the molecules to align antiparallel is determined by the ground state dipole moment. To calculate dielectric constants. where the actual measurement is the static dielectric constant of a series of solutions of varying weight fraction of the molecule in a non-polar solvent. The above equation assumes that the refractive index of a solution of the molecule has negligible dependence on its weight fraction.1.11 µ2 g = 3ε0 kT 9 M 2 0 NA (ε + 2)(n0 + 2) ρ0 ∂ ∂ω . o (4.5. The value is then extrapolated to infinite dilution to calculate the dipole moment using equation 4.9 The refractive index modulation achievable in a photorefractive guest host system depends on the figure of merit10 and in turn on the dipole moment of the material. ε0 .11 The refractive index of the solutions were measured using an Atago DRM2 refractometer and the variation with weight fraction was found to be negligibly small. ω is the weight fraction. The term (∂ /∂ω )0 represents the variation of dielectric constant with weight fraction at infinite dilution. NA is the Avogadro number and ε0 is the permittivity of vacuum.1) Here M is the molar mass of the molecule.98 Determination of ground state dipole moment (µg ) 4. so that the equation can be safely applied. As described in Section 1. The ground state dipole moment can be determined by the Debye Guggenheim method.

010 0.005 0. 2.4 2.3 2.000 0.4. If Cs is the capacitance with the solution and Ct is the capacitance with toluene. Plots of the variation of dielectric constant with weight fraction of the solute are shown in Fig.5 2.020 2.6 2.Determination of ground state dipole moment (µg ) 99 (d) using an HP 4277A LCZ meter operating at 10 KHz. The parameter ∂ /∂ω was extracted from the plot of dielectric constant with weight fraction of the molecule.0 0.1 2. Capacitance of the capacitor was measured in this manner first filling it with the solution under test and later with spectroscopic grade toluene.2 2. 4.015 0.4 2. Ks is the slope of the plot of Cs with 1/d and Kt is the slope of the plot of Ct with 1/d.2 2. Toluene ( r = 2.000 0.2) Here εt is the dielectric constant of toluene.020 Weight fraction of solute Weight fraction of solute Figure 4. εs was determined using equation 4.5.7 and 4. The dielectric constant of the solution. Equation 4.1 was used to calculate the ground state dipole moment of the molecule.4: Variation of the dielectric constant with weight fraction of 1a and 2a.8.2.0 0.005 0.015 0.379) was used for the standardization of the measurement. the dielectric constant of the solution can be determined from the ratio of the slopes of the plots of C vs 1/d.6.3 2. 4. εs = εt Ks Kt (4.1 2.5 Dielectric constant Dielectric constant 2.010 0. . 4.6 2. 4.

40 2.015 0.2 2.50 2.010 0.005 0. 3.5 2.8 Dielectric constant 2.005 0.6 2.020 Weight fraction of solute Weight fraction of solute Figure 4.000 0.010 0.015 0.0 2.7 2.6: Variation of the dielectric constant with weight fraction of 2d and 2e.45 2.010 0.100 2.2 2.6 dielectric constant 0.005 0.0 0.000 0.010 0.1 0.005 0.4 2.5: Variation of the dielectric constant with weight fraction of 2b and 2c.7 2.000 0.000 0.30 2.5 2. As the method assumes the values at infinite dilution.015 0. this change in concentration will not affect a comparison of the results.3 2.15 0.020 Weight fraction of solute Weight fraction of solute Figure 4.3 2.8 2.4 2.6 Dielectric constant 2. The range of weight fractions of the second set of molecules was less than the previous set.020 Dielectric constant 2.11 .25 2.55 Determination of ground state dipole moment (µg ) 2.2 2.0 2.015 0.020 2.35 2.4 2.1 2.20 2.

005 0.005 0.50 2.480 Dielectric constant 0.009 2.005 0.6 Dielectric constant 0.003 0.005 0.45 2.002 0.56 0.8: Variation of the dielectric constant with weight fraction of 3c and 3d.008 0.62 Dielectric constant 2.2.008 0.009 Weight fraction of solute Weight fraction of solute Figure 4.007 0.33564x10−30 C.4 0.009 Weight fraction of solute Weight fraction of solute Figure 4.7 2.008 0.7: Variation of the dielectric constant with weight fraction of 3a and 3b.004 0.007 0.475 2.55 101 2.006 0.004 0. 2.64 2. . A unit conversion can be achieved by noting that 1 Debye = 3.58 2.490 2.001 0.5 2.004 0.8 2.m = 10−18 esu.003 0.008 0.004 0.006 0.003 0.006 0.465 2.009 2.460 0.60 2.40 2.007 0.003 2.007 0.485 Dielectric constant 2.470 2. The results obtained are given in Table 4.Determination of ground state dipole moment (µg ) 2.006 0.

2: Ground state dipole moments of the molecules Molecule 1a 2a 2b 2c 2d µg (D) 9.47 4. arises from the polarization of the surrounding solvent molecules due .4. and shape of absorption or emission bands of a molecule due to the change in polarity of the solvent.63 4.102 Determination of excited state dipole moment (µe ) Table 4. The determination of excited state dipole moment is very important and there are many methods proposed in the literature.13 The spectral shift is caused by the electric field experienced by a molecule embedded in such a solvent.06 Molecule 2e 3a 3b 3c 3d µg (D) 12. Gas-phase stark effect is one of such methods which involve examination of the splitting of rotational lines due to externally applied electric field. the charge transfer is also very large provided the bond length remains unaltered upon excitation.78 8.12 A simple method is to analyze the solvent polarity dependence of the absorption and emission maxima (solvatochromism) of the molecule under consideration to extract µe .9 4. called reaction field. If the difference between the ground and excited state dipole moments is very large.88 8.4 Determination of excited state dipole moment (µe ) The excited state dipole moment is another quantity which shows the extent of charge transfer after excitation by radiation of sufficient energy.1 The solvatochromic effect Solvatochromism is the change in the position.85 7.20 8.43 11. This electric field.48 10.75 16. intensity.

υa + υf = −m2 {F (ε. The absorption and fluorescence spectra in solvents of varying polarity were needed for the analysis. (4.4 and 4. There are mainly two methods proposed in the literature for the analysis of the solvatochromic data.12 The solvatochromic method was used for the estimation of the first hyperpolarizability of the molecules. the emission υf cm−1 and absorption υa cm−1 bands are analyzed based on the following equations. The refractive index and the dielectric constant of the mixture at various proportions were measured to compute the bulk solvent polarity parameter F (ε.8 A polar molecule has unequal sharing of electrons between the atoms constituting it.2 Solvatochromic measurements The solvatochromic estimation of µe involves no laser measurements. In order to get a gradual variation of the polarity of the solvents.3) here n and ε are the refractive index and the dielectric constant of the mixture respectively.15 υa − υf = m1 F (ε.4) (4. a binary solvent mixture comprising the polar solvent acetonitrile and the non-polar solvent toluene were used for the solvatochromic analysis. n) .Solvatochromic measurements 103 to the dipole moment of the solute.5 show that the plots of υa −υf and υa +υf with F (ε. 4.4. n) = (2n2 + 1) (n2 + 2) (ε − 1) (n2 − 1) − (ε + 2) (n2 + 2) .2.3.5) here g(n) is another parameter given by g (n) = (3/2)(n4 − 1)/(n2 + 2)2 . For this purpose the experiment was well suited. F (ε. Equations 4. 4.1 Method 1 In this method.4. Although the accuracy of the method was less compared to more accurate methods like second harmonic generation or hyper Raleigh scattering. the purpose was to screen the synthesized chromophores. (4. n) + Constant. n) defined14 by equation 4. n) + 2g (n)} + Constant.

8.7) hca3 where h is the Planks constant and c is the velocity of light. shows a large solvatochromic effect.4. the analysis is based on the dimensionless solvent T proposed by Reichardt. These slopes are further given by. n) and [F (ε.7 .8) 32. where x = m2 /m1 .6) 2 (µ2 e − µg ) . This reduced the error due to the presence of impurities in the tion of EN T EN = . and λmax corresponds to the peak wavelength in the red region of the intramolecular charge transfer absorption of the molecule 2. The excited state dipole moment of the molecule can be expressed in terms of the known value of the ground state dipole moment as µe = µg (1 + x)/(x − 1). n) + 2g (n)].2.4. m1 = 2 (µe − µg )2 hca3 (4.13 This molecule.6-diphenyl-4-(2. Even small errors in the estimated value of the cavity radius can lead to very large errors as the value enters as cubed in the above equations. ET (solvent) − 30. The absorption maxima of the dye in solvent mixtures of varying polarity were experimentally determined and used for the calculaT .6-triphenyl-N-pyridino) phenolate.4 where ET (solvent) = 28591/λmax (nm).104 Solvatochromic measurements and [F (ε.13 which is given by equapolarity parameter EN tion 4.2 Method 2 In the second method. (4. m2 = 2 4. also called Reichardt’s dye. n) + 2g (n)] would be linear with slopes m1 and m2 respectively.16 Values of m1 and m2 can be obtained from the plots of υa − υf and υa + υf with F (ε. a is the Onsager cavity radius which can be calculated using the density (d) and the molecular weight (M) of the molecule using the relation a3 = (3M/4πdNA ). Taking the ratio m2 /m1 enables the determination of the excited state dipole moment without using the value of a. (4.

in cm−1 .17 Figure 4. Variation of (υa − υf ) with EN T was linear with more than 98 % correlation to a linear fit.Solvatochromic measurements 105 mixture as each solvent mixture was separately analyzed for its polarity value before use. Detailed physical properties of the toluene-acetonitrile mixture is available in the literature. the Stoke’s shift υa − υf was calculated from the absorption and fluorescence spectra. The variation of the Stoke’s shift with EN T is shown in Fig. 4. only solvent mixtures showing a linear variation of the polarity parameters were used.10 for the molecules 1a. Here υa and υf denote the absorption and fluorescence band maxima respectively. T and F (ε. The plots were nonlinear when the percentage of toluene was higher.11. 2a. thus for the analysis of the data. 4. n) versus the weight fraction of Acetonitrile The plots of EN in the mixture is shown in Fig. The Stoke’s shift (υa − υf ) was analyzed as a function of the polarity of the solvent. 4.9: Variation of the polarity parameters with weight fraction of Acetonitrile For the determination of the excited state dipole moment µe . 2c. . For the other set of molecules the variation is given in Fig.9. 2d and 2e. 2b.

50 Figure 4. 2d and 2e.44 ET N 0.48 0.38 0.40 0.44 ET N νa-νf cm 4000 3800 3600 0. 2a.42 0.38 0.46 0.50 0.42 0. 3c and 3d.50 0.106 4400 4200 -1 Solvatochromic measurements 1a 2a 2b -1 4400 4200 νa-νf cm 2c 2d 2e 4000 3800 3600 3400 0.48 0.44 ET N 4200 4000 3c 3d 3a 3b va-vf cm -1 va-vf cm 3800 3600 3400 -1 0.11: Graphs showing the linear variation of Stoke’s shift with EN T for 3a.50 Figure 4.48 0.40 0.46 0. The Stoke’s shift is related to the difference in dipole moments and the Onsager radii of the molecule and the dye by equation 4.48 0. In the expression. 4200 4000 3800 3600 3400 0.9) Here ∆µ = µe − µg is the difference between the ground and excited state dipole moments of the molecule being studied and ∆µD is that of Reichardt’s dye. 2c. As the values of aD and ∆µD . 2b.42 0.38 0.40 0.38 0.46 0.44 ET N 0. υa − υf = 11307.10: Graphs showing the linear variation of Stoke’s shift with EN T for 1a.40 0.6 ∆µ2 a3 D 3 ∆µ2 Da N ET + Constant (4. the Onsager radii of both the dye (aD ) and the molecule (a) enters as a ratio and thus the error due to the uncertainty in the value of a is minimized.9.42 0.46 0. 3b.

one can estimate the first hyperpolarizability of the molecule with the two level microscopic model of β .6.12 Molecule 2e 3a 3b 3c 3d µe (D) 19. It is assumed that the molecules have the donor and acceptor groups located such that the charge transfer takes place primar- . calculated from the area under the absorption band. β= 2 (µ − µ )µ2 3ωeg e g eg 2 − 4ω 2 )(ω 2 − ω 2 ) 2¯ h2 (ωeg eg (4. 18 In this model.50 17.3: Excited state dipole moments of the molecules estimated from the solvatochromic analysis.53 14.58 22.11 The solvatochromic method gives only one dominant component of the tensor quantity βijk .6 The area was determined by doubling the area of half of the absorption band if the spectrum was not symmetric about the peak frequency. the contributions from all excited states other than the first excited state are neglected.2˚ A and 9D respectively13 ). with EN Table 4.10) here ωeg = 2πc/λmax and µeg = the transition moment.96 14.Estimation of the first hyperpolarizability (β ) 107 were known (6.55 15.3.67 4.88 24.5 Estimation of the first hyperpolarizability (β ) Based on the solvatochromic measurements described above. Molecule 1a 2a 2b 2c 2d µe (D) 14.56 14.07 9. Results of the calculation are given in Table 4. the excited state dipole moment of the material under study could be evaluated from the plot of υa − υf T .6 The following equation gives the value of β in terms of experimentally measurable quantities.

74 4.77 5.17 2. All molecules showed an increase in dipole moment on excitation by light. Chromophores for such photorefractive guest host systems must not be absorbing at the operating wavelength to get an effective two beam coupling gain.4.77 3.42 3.6 Summary and conclusions The purpose of the work outlined was to evaluate the nonlinear optical properties of the synthesized molecules so as to select those possessing high values of photorefractive figure of merit.20 4.4: Compilation of the results obtained on the different molecules Molecule 1a 2a 2b 2c 2d 2e 3a 3b 3c 3d λmax (nm) 387 393 395 397 398 399 400 400 401 402 β (10−30 ) esu 3.63 1. This showed that there was a higher degree of charge transfer taking place.6 Thus Eq.87 3.84 2. Table 4.16 4. Photorefractive materials can be used for beam amplification in the two beam coupling geometry.20 3.14 4.57 2.07 2.10 gives βxxx (or βCT ) (charge transfer).56 9µg β (10−46 ) esu 3.64 5.19 The molecules described here have only low absorption in the visible region of the spectrum. 4.74 4.97 2.32 2. The ground and excited state dipole moments were determined which gave insight into the possibility of . The results are given in Table 4.22 2.108 Summary and conclusions ily along the axis of the permanent ground state dipole moment of the molecule.

2. The chromophores with odd number of alkyl spacers showed higher (βijk ) values. It is reported that the length of the alkyl spacer connecting the donor to the acceptor moiety has major effect on the value of (βijk ). This was stimulated by the fact that for highly efficient photorefractive applications. as shown in Table 4. There was only small change in the absorption peak of the these materials. The main aim of the present work was to study the possibility of the synthesized molecules for application to photorefractive polymers as the absorption of these molecules do not fall well in to the visible region. each time before use.4. The .Summary and conclusions 109 light induced charge transfer in these molecules. This molecular parameter was kept in mind when deciding the requirement of poling for the photorefractive samples. but a steady increase in hyperpolarizability was not achieved. the molecule for electro-optic functionality should not absorb at the operating wavelength. errors can be neglected even if it is as high as 20%. The solvatochromic method assumes that the molecule is spherical and this method is suitable to small molecules. Measures were taken to reduce the errors by using solvents of maximum purity and they were characterized as described in Section 4. the charge redistribution was such that it resulted in a higher value for the dipole moment. 21 A deep investigation of this interesting effect was not attempted. on excitation by light.4.2. The estimation of (βijk ) suffers from errors associated with the Onsager radius and the size of the molecule though some of them can be circumvented by appropriate processing of the data. It is reported that the lower values for even number of alkyl units can be due to a centrosymmetric arrangement of the molecules. It could be seen that. As the aim was to screen the molecules to find the ones with maximum value for (βijk ).20 This approach of increasing the value of β has the advantage that the absorption maxima of the molecule is not getting changed as there is no change in the effective conjugation length of the material. A small increase in the figure of merit was observed.20. The estimate of the ground state dipole moment gave the relative tendency of the investigated molecules to align antiparallel in pairs in the bulk so that a net second order nonlinear optical effect could be absent.

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