Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 186–190

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Spectral and computational studies in substituted pyrrolyl styryl ketones

– Assessment of substituent effects
R. Rajalakshmi ⇑, D. Chinnaraja, J. Jayabharathi
Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamilnadu, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 o, m and p-methoxy substituted 2-

pyrrolyl styryl ketones were
synthesized.
1 13
 UV, IR, H, C NMR of the compound
1–4 was compared.
 Conformation of the synthesized
compound is conformed as anti.
 NBO, NLO and HOMO–LUMO analysis
were carried out.

a r t i c l e i n f o a b s t r a c t

Article history: A series of newly synthesized potent bioactive 2-pyrrolyl styryl ketone derivatives were characterized by
Received 27 April 2013 spectral techniques. The effect of substituent on the absorption maximum, IR stretching frequencies and
Received in revised form 29 July 2013 NMR chemical shifts were investigated. DFT calculations were made to calculate HOMO–LUMO energies
Accepted 2 August 2013
and natural bond orbital analysis [NBO]. The electric dipole moment (l) and the hyperpolarisability (b) of
Available online 9 August 2013
the investigated molecules have also been studied and found that these synthesized molecules exhibits
microscopic non-linear optical (NLO) behavior with non-zero tensor components.
Keywords:
Ó 2013 Elsevier B.V. All rights reserved.
UV
IR
NMR
NLO
HOMO–LUMO

Introduction tion. For these systems, optimization of the p-conjugated bridges,

A general approach for obtaining materials with important non-
linear optical properties consists in the synthesis of chromophores
involving electron-donor and electron-acceptor groups linked
through a p-conjugated spacer, so called D–p–A systems [1]. The
efficient intramolecular charge transfer (ICT) along the p-conju-
gated bridges of these organic systems is particularly relevant in
the development of non-linear optical [NLO] materials since,
amongst other properties nearly instantaneous electronic polariza-
⇑ Corresponding author. Tel./fax: +91 4144 238282, mobile: +91 98943 85181.
E-mail address: chemrajalaksmi@gmail.com (R. Rajalakshmi).
electron-donor and electron-acceptor characteristics of the substit-
uents are needed to obtain the highest nonlinearities at a molecu-
lar level [2]. One approach currently being explored by many
researchers is to substitute the benzene rings typical of these D–
p–A systems with an electron rich and/or electron poor aromatic
ring that can act as an auxiliary donor/acceptor while modulating
the p-conjugated bridges. Experimental studies have demon-
strated that replacing the benzene ring of a chromophore with eas-
ily delocalizable five-membered heteroaromatic rings, such as
thiophene, pyrrole and thiazole, results in an enhanced molecular
hyperpolarizability [3,4]. Recent theoretical calculations suggest
that heterocyclic rings play a subtle role in the second-order NLO

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.08.003
 R. Rajalakshmi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 186–190
properties of donor–acceptor compounds. The effect of substitu-
ents on the infrared carbonyl frequencies, the proton and carbon-
13 chemical shifts in several chalcones and on CAH, C@C, CH@CH
in some alkenes have been investigated [5-10]. A similar study
involving styryl pyrrolyl ketone is utmost unknown. Hence, the
ortho-, meta- and para-methoxy substituted 2-pyrrolyl styryl ke-
tones were prepared with a view to study the effect of substituent
on their ultraviolet, infrared, proton and carbon-13 NMR resonance
spectra and photophysical behavior in these styryl pyrrolyl ke-
tones. DFT calculations were made to analyze HOMO–LUMO ener-
gies, NBO and hyperpolarisability behavior.
Results and discussion
Infrared spectra
Normally chalcones show two carbonyl bands for S-cis and S-
trans conformers in solution. Although an equilibrium mixture of
different conformations of some of the chalcones may exist in solu-
tion, it is likely that only one form can exist in the crystalline state.
In addition to carbonyl, the system under investigation also shows
strong band due to the secondary amino (>N–H) group that is pres-
ent in the pyrrole moiety of the system.
The carbonyl (1649.81 cm11) stretching frequency of the 2-
pyrrolyl styryl ketones is lowered (1645.03 cm11) when a powerful
electron donating group is present in the phenyl ring. This may be
due to the fact that electron donating group reduces the double bond
character of the carbonyl band and thereby lower the frequency.
Even though the effectiveness is similar in ortho and para positions
the increase in carbonyl absorption frequency is attributed to the
loss of co-planarity of styryl group with the carbonyl group.
NMR spectra
In most of the cases, since the absorption of the olefinic protons
in the chalcones is also in the aromatic region, it is quite difficult to
differentiate the olefinic proton signals from that of the aryl pro-
tons. Generally of the two olefinic protons in chalcones, the one
nearest to the aromatic ring (Hb proton) resonates in the deshiel-
ding region compared to that of a-proton (Ha). Because this will
experience a magnetic field from the induced circulation of p elec-
trons in the aromatic ring, which will augment the applied field and
hence lead to a higher d value. The substituent chemical shift for the
Hb proton signal is less sensitive when the substituents are in meta-
or -para position. The Hb proton shift for the above mentioned sub-
stituents always lie in 7.6–7.9 ppm region when the substituents
are in the-ortho position, the Hb proton signals are obtained in the
downfield (8.225 ppm region)compared to their-para counterpart.
In these cases there may be some interaction between the Hb
protons and the ortho-substituents. In such a system there will
be two opposite effects the ortho-substituent may push Hb proton
out of the plane of the aromatic ring and this will cause less desh-
ielding by the ring current effect. The close approach of the ortho-
substituents and the b protons will deshield the proton. This effect
arises from the distortion of the electronic cloud around Hß protons
when the two atoms approach within the sum of their Van der
Waals radii and can apply to Hb protons. The same trend in chem-
ical shift value is observed irrespective of the nature of electrical
effects of substituent in pyrrole ring.
The signals of the ethylenic protons in all the compounds inves-
tigated in the study are assigned. The ethylenic proton signals give
a doublet in most cases and are well separated from the signals of
the aromatic protons Hb and the secondary amino proton present
in the pyrrole ring gives only singlet (9.6–11.6 ppm). The
assignment of carbonyl peak in the spectra is very simple in all
187
the cases since it appears as a clear single peak in the region of
177.14–179.0 (ppm). The most striking feature of carbonyl carbon
resonance position for these chalcones is apparent due to lack of
sensitivity towards the variety of substituents.
In mono substituted styrenes, the resonance of Ca carbon falls
in a quite well defined region (133–138 ppm) [11]. In substituted
2-pyrrolyl styryl ketones the same carbon atom is considered as
Cb, whose chemical shifts fall in the region (138.07–147.54 ppm).
The other carbon of the ethylenic bond Ca lies relatively at high
field 124.49 ppm .Since, no pronounced variations are found for
compounds with ortho-substiuents compared to their para-coun-
terpart and the effect substituents on the Ca chemicals shifts of
these chalcones is negligible. But in the case of Cb carbons, there
are appreciable changes in the chemical shifts when ortho-substit-
uents are present in the styryl part compared with their para coun-
terpart. The pronounced difference in chemical shifts for Cb carbon
(Dd  3–4 ppm) may be due to the steric interference to co-plan-
narity of the styryl part in the o-substituted 2-pyrrolyl styryl ke-
tone. The difference in chemical shifts for Ca carbons is very
(Dd  1–2 ppm) low.
Conformational analysis
Generally in compounds capable of exhibiting geometrical
isomerism, the bulky group always adopts the Trans position.
Moreover comparison of the chemical shifts of ethylenic proton
in the styryl pyrrolyl ketone derivatives (1–4) with that of aldehy-
dic protons of their parent benzaldehydes (Table 1) reveals that
there occurs considerable shielding during the conversion of alde-
hyde into the corresponding styryl pyrrolyl ketone derivatives.
Therefore it is inferred that the two protons of the ethelenic system
are anti to each other. Hence, the favoured conformation of styryl
pyrrolyl ketone is predicted to be anti. In order to confirm the fa-
voured conformation, DFT calculations were made by using
B3LYP-631G(d, p) basis set for all the styryl pyrrolyl ketone deriv-
atives. The heat of formation values for their geometrical isomers
is given in Table 2 along with the dipole moment values. From
the heat of formation values (Table 2) it is predicted that the anti
conformation is the more favoured conformation for all the styryl
pyrrolyl ketones (1–4). The optimized structures of the favored
conformations are shown in Fig. S1.
Effect of solvents on the ultraviolet absorption spectra
The wavelength maxima (kmax) of the unsubstituted styryl
pyrrolyl ketone in eighteen selected solvents is listed in Table 3
Table 1
Comparison of chemical shifts of compound (1–4) with their corresponding aldehyde.
Substituent Parent aldehyde Shelding
H 7.84 10.02 2.16
2-OCH3 7.78 9.98 2.2
3-OCH3 7.80 9.98 2.18
4-OCH3 8.13 9.86 1.73
Table 2
Relative energies of geometrical isomers.
Substituent Energy(kcal/mol)
Trans Cis
H 0 2.04
o-OCH3 0 4.85
m-OCH3 0 5.02
p-OCH3 0 3.54
188 R. Rajalakshmi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 186–190

Table 3 n = 18; R = 0.910; SE = 0.049

Absorption maxima for 2-pyrrolyl styryl ketones in polar and non-polar solvents. In p ? p⁄ transition of 2-pyrrolyl styryl ketone the positive sign
S. no. Solvents kmax (nm) log kmax of co-efficient ‘S’ and ‘b’ indicates a hypsochromic shift with both
1. Methanol 336.17 2.5276
increasing the solvent polarity and hydrogen bond acceptor basi-
2. 2-Methyl-propan-2-ol 336.97 2.5276 city (a/S = 0.4886; b/S = 0.1238). The positive sign of co-efficient
3. Propan-1-ol 350.60 2.5322 ‘a’ indicates a hypsochromic shift with increasing solvent hydrogen
4. Benzyl alcohol 346.02 2.5391 bond donor acidity. Absorption of 2-pyrrolyl styryl ketone for
5. Butan-1-ol 339.60 2.5309
6. Butan-2-ol 338.06 2.5290
p ? p⁄ transition are compared with solvent parameters ET (30)
7. Propan-2-ol 336.43 2.5269 [18,19]. But the correlation of kmax of 2-pyrrolyl styryl ketone with
8. Ethanol 339.78 2.5312 ET (30) values are poor (r = 0.8481; A = 51.71; B = 20.645; n = 18).
9. Dioxane 327.79 2.5156 The poor correlation may be due to presence of hydrogen bonding
10. DMSO 341.97 2.5340
and change in geometry during excitation. The sizable solvatochro-
11. Ethyl acetate 326.81 2.5143
12. n-Hexane 317.31 2.5016
mic responses are indicative of highly polarizable p-conjugated
13. Acetonitrile 328.78 2.5169 structures.
14. Cyclohexane 320.04 2.5052
15. Pyridine 335.43 2.5256
Electric moments
16. Triethylamine 327.08 2.5146
17. Xylene 330.52 2.5192
18. Carbon tetrachloride 325.79 2.5129 The dipole moment of a molecule is an important property
mainly used to study the intermolecular interactions involving the
non-bonded dipole–dipole interactions, because higher the dipole
moment, stronger will be the intermolecular interactions. The calcu-
Table 4a lated value of dipole moment is found to be quite higher and the
The significant donor–acceptor interactions in compound 1and their second order frontier orbital energy gap is found to be very low. The very high di-
perturbation energies in kcal/mol. pole moments are manifested in its high reactivity and consequently
Donor Type Ed/e Acceptor Type Ed/e E2 Ej– Fi–j higher selectivity for the target carcinogenic/tumor cells. According
Ei to the present calculations, the first static hyperpolarisability b(tot)
C1AC2 p 1.7886 C3Ac4 p* 0.3149 31.84 0.49 0.115 of unsubstituted styryl pyroryl ketone (299.22  1031 e.s.u.) is rel-
C1AC2 p 1.7886 C10Ao15 p* 0.1728 35.02 0.54 0.124 atively smaller than o- and m-substituted styryl pyroryl ketones
C3AC4 p 1.8013 C1Ac2 p* 0.3575 44.32 0.50 0.138 (412.92  1031 and 819.30  1031 e.s.u.) but the hyperpolarisabil-
C16AC17 p 1.6400 C18Ac21 p* 0.3119 39.16 0.49 0.125
ity b(tot) of p-substituted styryl pyroryl ketone (61.091031 e.s.u.)
C16AC17 p 1.6400 C19Ac23 p* 0.3294 41.95 0.48 0.128
C18AC21 p 1.6656 C16Ac17 p* 0.3678 41.37 0.49 0.128 is still lowere than that of unsubstituted styryl pyroryl ketone. In
C18–27 p 1.6656 C19Ac23 p* 0.3294 42.20 0.49 0.128 addition to well known empirical rules to estimate qualitatively
C19AC23 p 1.6553 C16Ac17 p* 0.3678 43.24 0.48 0.130 the microscopic nonlinear response in 1–4, DFT calculation is a more
C19AC23 p 1.6553 C18Ac21 p* 0.3119 40.76 0.49 0.127 accurate prediction of the NLO activity [13]. From Table 4 it is sug-
N-5 p 1.6095 C1Ac2 p* 0.3575 57.71 0.51 0.154
N-5 p 1.6095 C3Ac4 p* 0.3149 72.59 0.50 0.174
gested that these compounds are polar having non-zero dipole mo-
0–15 p 1.9239 C1Ac10 p* 0.0495 22.50 1.18 0.146 ment, hyperpolarizabilities and hence found to possess a good
0.15 p 1.9239 C10Ac11 p* 0.0406 22.34 1.16 0.145 microscopic NLO behavior [14-16].

Natural Bond Orbital (NBO) analyses

*
and were compared with the p values for each solvent, as deter-
Several donor–acceptor interactions are observed in all the
mined by Kamlet and Taft [12]. Moderate to large positive solvato-
compounds (1–4) and among the strongly occupied NBOs, the
chromism was observed moving from n-hexane to DMSO solutions
most important delocalization sites are in the p system and in
for 2-pyrrolyl styryl ketone. The multiple linear regression analysis
the lone pairs (n) of the oxygen and nitrogen present on the styryl
of the spectroscopic data for 2-pyrrolyl styryl ketone for p ? p⁄
pyrrolyl ketone moiety. The r system shows some contribution to
transition in eighteen different solvents were carried out using
the delocalization and almost the donor–acceptor interactions are
the Eq. (5). The results of the regression analysis are given below.
same in these compounds. The important contribution to the delo-
log kmax ¼ h þ Sp þ aa þ bb ð5Þ calization corresponds to the donor–acceptor interactions are

¼ 2:505 þ 0:024231p þ 0:01184a þ 0:0030b LPN5 ? C3AC4 ? C1AC2, C16AC17 ? C18AC21, C1AC2,
ð0:00258Þ ð0:045Þ ð0:0036Þ þ ð0:004Þ LPN5 ? C3AC4, and LPO15AC10AC11 (Table 4). The charge distri-
bution shows that the more negative charge is concentrated on

Table 4b
The significant donor–acceptor interactions in compound 2and their second order perturbation energies in kcal/mol.

Donor Type Ed/e Acceptor Type Ed/e E2 Ej–Ei Fi–j

C2AH7 p 1.9486 C13AH14 p* 0.0431 22.38 1.14 0.143
C3Ac4 p 1.7712 C1Ac2 p* 0.3856 22.20 0.28 0.073
C8Ac21 p 1.6811 C19Ac23 p* 0.3543 21.29 0.28 0.069
NA5 lp 1.5706 C1Ac2 p* 0.3856 26.19 0.29 0.0178
NA5 Lp 1.5706 C3Ac4 p* 0.3560 45.47 0.28 0.103
oA15 lp 1.8961 C10Ac11 p* 0.0534 17.42 0.64 0.99
C19Ac23 p 1.6515 C16Ac17 p* 0.3696 19.96 0.29 0.668
C19Ac23 p 1.6515 C18Ac21 p* 0.3129 18.96 0.28 0.66
C18Ac21 p 1.6811 C16Ac17 p* 0.3696 19.74 0.28 0.068
C16Ac17 p 1.637 C18Ac21 p* 0.3129 19.87 0.28 0.067
C16Ac17 p 1.637 C19Ac23 p* 0.3543 19.94 0.27 0.066
 R. Rajalakshmi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 186–190 189

Table 4c Table 6
The significant donor–acceptor interactions in compound 3and their second order Dipole moment, polarizability and hyperpolarizabilty of compound 1–4.
perturbation energies in kcal/mol.
Substituent Dipolemoment Polarizability Hyperpolarizabilty
Donor Type Ed/e Acceptor Type Ed/e E2 Ej–Ei Fi–j l(tot) a(tot)  1023 b(tot)  1031
C1Ac2 p 1.7879 C3Ac4 p 0.3147 31.79 0.49 0.114 H 0.90 132.08 299.22
C1Ac2 p 1.7879 C10Ao15 p 0.1724 35.33 0.54 0.124 o-OCH3 0.75 428.86 412.92
C3Ac4 p 1.8004 C1Ac2 p 0.3578 44.50 0.50 0.138 m-OCH3 0.51 574.97 819.30
C11Ac13 p 1.9065 C10Ao15 p 0.1724 17.13 0.58 0.093 p-OCH3 0.84 603.03 61.09
C16Ac22 p 1.6771 C17Ac19 p 0.3101 32.51 0.50 0.117
C16Ac22 p 1.6771 C18Ac29 p 0.3544 32.50 0.48 0.134
C17Ac19 p 1.6919 C16Ac22 p 0.3524 45.99 0.49 0.135 The 3D plot of HOMO–LUMO orbital picture is displayed in Fig. S2.
C17Ac19 p 1.6919 C18Ac29 p 0.3545 45.99 0.49 0.114 It is evidenced that all the 2-pyrrolyl styryl ketone derivatives are
C18Ac29 p 1.6655 C10Ac22 p 0.3524 32.67 0.50 0.139
highly polar and are expected to possess non-linear optical proper-
C18Ac20 p 1.6655 C17Ac19 p 0.3101 47.41 0.30 0.139
N-5 p 1.6097 C1Ac2 p 0.3578 57.54 0.51 0.154 ties. Analyses of NLO behavior of the synthesized compounds are
N-5 p 1.6097 C3Ac4 p 0.3147 72.62 0.50 0.174 currently in progress.
o-15 Lp 1.9238 C1Ac10 p 0.0493 22.45 1.18 0.146
o-15 Lp 1.9811 C10Ac11 p 0.0407 22.40 1.16 0.145
o-24 Lp 1.895 C18Ac29 p 0.3545 34.72 0.66 0.144
Conclusion

The effect of an electron donating substituent on the UV, infra-

red, proton and carbon-13 nuclear magnetic resonance spectra of
styryl pyrrolyl ketones have been investigated. The NBO, NLO
Table 4d
The significant donor–acceptor interactions in compound 4and their second order
and HOMO–LUMO analysis were carried out theoretically and ana-
perturbation energies in kcal/mol. lyzed. From the spectral and computational studies it is concluded
that the substituent on the ortho and meta position of the phenyl
Donor Type Ed/e Acceptor Type Ed/e E2 Ej–Ei Fi–j
ring exert similar electrical effects on the system investigated but
*
C2AH7 p 0.9742 C3AH14 p 0.0218 11.22 1.15 0.144 the para-substituted compound shows pronounced variation when
C3Ac4 p 0.8874 C1Ac2 p* 0.1907 11.02 0.28 0.073
C16Ac17 p 0.8096 C18Ac20 p* 0.1712 10.86 0.27 0.068
compared to ortho and meta-substituted compounds.
C18Ac20 p 0.8288 C19Ac22 p* 0.1690 19.71 0.32 0.101
C19Ac22 p 0.8415 C16Ac17 p* 0.2148 14.41 0.26 0.80 Experimental
N-5 p 0.7862 C1Ac2 p* 0.1904 12.95 0.29 0.078
N-5 p 0.7862 C3Ac4 p* 0.1789 22.73 0.28 0.103
o-25 p 0.0001 C16Ac17 p* 0.2148 12.82 0.31 0.086 Materials and methods

2-Acetyl pyrrole (Sigma–Aldrich Ltd.), substituted benzalde-

hydes (S.D. fine.) and all the other reagents used without further
hetero atoms whereas the partial positive charge resides at purification.
hydrogens.
Spectral measurements
IR spectra were recorded in KBr (pellet forms) on a Thermonic-
HOMO–LUMO energies by DFT method
olet AVATAR 330 FT-IR spectrometer (mmax in cm1). 1H NMR spec-
tra were recorded at 400 MHz on Brucker AMX 400 MHz
The optimized energy, dipole moment and HOMO–LUMO ener-
spectrophotometer using CDCl3/DMSO as solvent and TMS (Tetra-
gies of the compounds (1–4) were calculated theoretically and are
methyl silane) as internal standard 13C NMR spectra were recorded
given in Table 5. From the HOMO–LUMO analysis it is clear that the
at 75 MHz on Brucker AMX 300 MHz spectrophotometer using
intra molecular charge transfer must occur within the molecule.
CDCl3 as solvent.
Recently the energy gap between highest occupied molecular orbi-
tal (HOMO) and the lowest un occupied molecular orbital (LUMO)
Computational details
have been used to prove the bioactivity from intramolecular charge
Quantum mechanical calculations were used to carry out the
transfer (ICT) [17,18]. From the HOMO–LUMO orbital picture of
optimized geometry, NLO, NBO and HOMO–LUMO analysis with
unsubstituted styryl pyroryl ketones, it is observed that the filled
Guassian-03 program using the Becke3–Lee–Yang–Parr (B3LYP)
p orbital (HOMO) entirely located on the pyrrolyl ring. In case of
functional supplemented with the standard 6-31G (d, p) basis set.
o- and m-methoxy substituted styryl pyrrolyl ketone, the filled p
As the first step of our DFT calculation for NLO, NBO and HOMO–
orbital (HOMO) mostly located on the aldehydic ring but the
LUMO analysis, the geometry taken from the starting structures
HOMO in the p-OCH3 substituted styryl pyrrolyl ketone is mostly
were optimized and then, the electric dipole moment l and b ten-
located in the pyrrolyl ring and partly on the aldehydic ring. The
sor components of the studied compounds were calculated, which
unfilled p* orbital in 1–4 (LUMO) is located on the entire molecule.
has been found to be more than adequate for obtaining reliable
The introduction of the electron-donating substituent into the
trends in the first hyperpolarizability values.
phenyl ring raises the energy of the highest occupied molecular
We have reported the btot (total first hyperpolarizability) for the
orbital (HOMO). From the dipole moment values given in Table 6.
investigated molecules and the components of the first hyperpo-
larizability can be calculated using equation:
Table 5
X
HOMO–LUMO energies of compound 1–4.
bi ¼ biii þ 1=3 ðbijj þ bjij þ bjji Þ ð1Þ
i–j
Substituent HOMO (kJ/mole) LUMO (kJ/mole)
Using the x, y and z components, the magnitude of the first hyper-
H 235.32 50.79
polarizability tensor can be calculated by
2-OCH3 232.49 3.58
3-OCH3 235.35 3.57  1=2
4-OCH3 154.52 48.64 btot ¼ b2x þ b2y þ b2z ð2Þ
190 R. Rajalakshmi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 186–190
The complete equation for calculating the magnitude of first
hyperpolarizability from Gaussian-03 output is given as follows:
h i1=2
btot ¼ ðbxxx þ bxyy þ bxzz Þ2 þ ðbyyy þ byzz þ byxx Þ2 þ ðbzzz þ bzxx þ bzyy Þ2
All the electric dipole moment and the first hyperpolarizabilities are
calculated by taking the Cartesian coordinate system
(x, y, z) = (0, 0, 0) at own center of mass of the compound.
Natural Bond Orbital (NBO) analysis
NBO analysis have been performed on the molecule at the DFT/
B3LYP/6-31G (d, p) level in order to elucidate the intermolecular,
rehybridization and delocalization of electron density within the
molecule. The second order Fock matrix was carried out to evalu-
ate the donor–acceptor interactions in the NBO analysis. The inter-
actions result is a loss of occupancy from the localized NBO of the
idealized Lewis structure into an empty non-Lewis orbital. For each
donor (i) and acceptor (j), the stabilization energy E(2) associated
with the delocalization i ? j is estimated as
2 [8] E. Solcaniova, S. Toma, Org. Magn. Reson. 14 (1980) 138–140.
Fði; jÞ
Eð2Þ ¼ DEij ¼ qi
ej  ei
where qi is the donor orbital occupancy, ei and ej are diagonal ele-
ments and F (i, j) is the off diagonal NBO Fock matrix element. The
larger the E(2) value, the more intensive is the interaction between
electron donors and electron acceptors, i.e., the more donating ten-
dency from electron donors to electron acceptors and the greater
the extent of charge transfer or conjugation of the whole system.
General procedure for the synthesis of 2-pyrrolyl styryl ketone
derivatives
2-pyrrolyl styryl ketone derivatives were synthesized by heating
a mixture of benzaldehyde or substituted benzaldehyde and 2-
acetyl pyrrole in aqueous ethanol (60%; 150 ml) containing sodium
hydroxide (1 g) over a water bath for half an hour and recrystal-
lized from ethanol as glittering solid [19]. The experimental data
of of 2-pyrrolyl styryl ketone derivatives are given in Supplemental
part (S3).
ð3Þ
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2013.08.003.
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