Accepted Manuscript

Synthesis, characterization and intramolecular proton transfer of 3,3’-Dihy-

droxy-4,4’-[5-methyl-1,3-phenylenebis(nitrilomethylidyne)]-bis-phenol

Hossein Eshtiagh-Hosseini, S. Ali Beyramabadi, Ali Morsali, Masoud Mirzaei,

Hamed Chegini, Morteza Elahi, Mohammad Ali Naseri

PII: S0022-2860(14)00462-1
DOI: http://dx.doi.org/10.1016/j.molstruc.2014.05.003
Reference: MOLSTR 20602

To appear in: Journal of Molecular Structure

Received Date: 2 November 2013

Revised Date: 30 April 2014
Accepted Date: 2 May 2014

Please cite this article as: H. Eshtiagh-Hosseini, S. Ali Beyramabadi, A. Morsali, M. Mirzaei, H. Chegini, M. Elahi,
M.A. Naseri, Synthesis, characterization and intramolecular proton transfer of 3,3’-Dihydroxy-4,4’-[5-methyl-1,3-
phenylenebis(nitrilomethylidyne)]-bis-phenol, Journal of Molecular Structure (2014), doi: http://dx.doi.org/
10.1016/j.molstruc.2014.05.003

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 Synthesis, characterization and intramolecular proton transfer of 3,3'-
Dihydroxy-4,4'-[5-methyl-1,3-phenylenebis(nitrilomethylidyne)]-bis-
phenol

Hossein Eshtiagh-Hosseinia, S. Ali Beyramabadib,*, Ali Morsalib, Masoud Mirzaeia, Hamed

Cheginib, Morteza Elahib, Mohammad Ali Naseric

a
Department of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran

b
Department of Chemistry, Mashhad branch, Islamic Azad University, Mashhad, Iran

c
Department of Chemistry, Faculty of Science, Birjand University, Birjand, Iran

* Corresponding author (Beyramabadi):

Tel.: +98 511 8414182; fax: +98 511 8414182

E-mail addresses: beiramabadi@yahoo.com, beiramabadi6285@mshdiau.ac.ir.

1
Abstract

A newly synthesized Schiff base, 3,3'-Dihydroxy-4,4'-[5-methyl-1,3-

phenylenebis(nitrilomethylidyne)]-bis-phenol, was characterized experimentally. Its

geometries optimization, tautomerization, assignment of the IR bands and NMR chemical

shifts were calculated by using density functional theory (DFT) method. In addition, the

Atoms in molecules (AIM) analysis was employed for investigation of its tautomerization.

Four possible tautomers of the investigated Schiff base were optimized in both of the gas and

solution phases. The Schiff base has no planar structure, but each of the benzene rings is in a

separate plane. In the most stable tutomer, the phenolic protons of the two –OH groups are

engaged in the intramolecular-hydrogen bond with the azomethine nitrogens. Good

consistency between the theoretical and experimental results confirms validity of the

optimized geomrtry. Also, kinetics and mechanism of the intramolecular-proton transfer of

the studied Schiff base was demonstrated theoretically.

Keywords: Schiff Base; DFT; Assignment; Intramolecular Proton Transfer, AIM analysis,

Tautomerization.

2
1. Introduction

The Schiff bases and their metal complexes have a large number of applications especially in

the fields of biochemistry, catalyst, synthesis and as an intermediate in a number of

enzymatic reactions [1–4]. The tetradentate ONNO donor Schiff bases form a main group of

compounds, salen or salophen, which serve in a wide variety of applications [5].

Hydrogen bond systems are one of the key interactions that determine the structure,

functionality, and dynamic processes in a large kind of systems. Therefore, the

understanding and comprehensive studies of the nature of hydrogen bonds is important for

biological and chemical systems [6].

In view of our interest in synthesis of new Schiff bases [7-14], herein we report synthesis,

experimental and theoretical characterization of a new Schiff base, 3,3'-Dihydroxy-4,4'-[5-

methyl-1,3-phenylenebis(nitrilomethylidyne)]-bis-phenol = L. In addition, tautomerism of

the L was investigated using the DFT approaches.

In the structure of the titled compound, there are two OH…N intramolecular-hydrogen

bonds, competition of which has important role in stability of the tautomeric structures. A

major aim of this paper is to study hydrogen bonding in aminohydroxyaryl Schiff bases and

to theoretically describe the proton-transfer process and particular tautomeric forms, too.

2. Experimental

2.1. Material and methods

All of used chemicals were obtained from Merck Company and were used without any

further purification. Melting points were determined using an electrothermal 9100 melting

point apparatus. The IR spectra were obtained using a Buck 500 infrared spectrophotometer.

3
Elemental analysis (C, H, N) was performed on a Heraeus elemental analyzer CHN-O-

Rapid. The 1H and 13

C NMR spectra were obtained on a Bruker Drx-500 Avance

spectrometer (500.13 MHz) in DMSO. Mass spectra were recorded on a Shimadzu-GC-

Mass-Qp 1100 Ex.

2.2. Synthesis of the titled Schiff base (C21H18N2O4)

A solution of 2.36 g (6.66 mmol) 3-methylbenzene-1,2-diamine and 1.88 g (13.61 mmol) of

dihydroxybenzaldehyde in toluene (150 mL) was refluxed under vigorous stirring with a

Dean-Stark for 3 h. The resulting suspension was kept at room temperature prior to being

filtered, washed with ethanol (2×10 mL) and dried with diethyl ether (2×10 mL) to afford a

deep red solid. The solid was recrystallized for further purification. (Yield: 65%, m.p.> 250

°C, the molecular ion peaks, m/z (M+) =363).

3. Computational details

The DFT clculations have been performed using B3LYP functional [15] as implemented in

the Gaussian 03 program package [16]. The 6-311+G(d,p) basis set was used. Here, the

Polarizable-Continuum Model (PCM) [17] has been employed for investigation of solute-

solvent interactions. All geometries were fully optimized in both of the gas phase and

methanolic solution. The optimized geometries were used to calculate the vibrational

frequencies, NMR chemical shifts and AIM analysis.

The 1H and 13
C NMR chemical shifts were predicted with respect to tetramethylsilane

(TMS), where the GIAO method was used [18]. Since the DFT-calculated vibrational-

frequencies are usually higher than the experimental ones, they were scaled using a factor of

0.9614 [19].

4
 The AIM topological analysis was performed in accordance with Bader’s approach [20]

using AIMall package [21]. The DENSITY= CURRENT option was used to generate the

wavefunction files.

3. Results and discussion

3.1. Tautomerism

There are four possible tautomers for the titled compound, geometries of which are fully

optimized in both of the gas phase and methanolic solution. Their PCM optimized structures

are shown in Fig. 1, which are named as La, Lb, Lc and Ld.

5
 H8 La H3 O3 H4
H9 O4

C10 C9 C2 C3

O2 O1 C1 C4 H5
H10 C11 C8
H1 C6 C5
C12 C13 H2
H18 H6
H11 N1 C7
C14 N2
C20 H7
H12 C19 C15

C18 C16
H17 H13
C17 C21
H14
. H16 H15

6
Figure 1. The B3LYP optimized geometries of the La, Lb, Lc and Ld tautomers of the titled
Schiff base.

In continuation, the tautomerization of the titled Schiff base was investigated using the

PCM model. Otimized geometries of the transition states are shown in Fig. 2.

The La tautomer is more stable than the Lb, Lc and Ld tautomers by15.27, 30.58 and

29.66 kJ.mol-1 in the gas phase and 3.38, 5.90 and 10.95 kJ.mol-1, in the PCM model,

⎯⎯
→ Lb tautomerization involves the TSLa-Lb as the transition state.
respectively. The La ←⎯
⎯

In this tautomerism, the intramolecular-proton transfer (IPT) from O2 to N2 atom is

occurring by activation energy (Ea) of 12.12 kJ.mol-1 in the gas phase, which reduces to 5.66

kJ.mol-1 by considering the solvent effects in PCM model.

7
 ⎯⎯
→ Lc tautomerism is in competition with the La ←⎯
The La ←⎯
⎯ ⎯⎯
→ Lb one. The former
⎯

⎯⎯
→ Lc pathway is higher than the
involves the TSLa-Lc transition state. The Ea of the La ←⎯
⎯

⎯⎯
→ Lb one by 8.04 and 1.69 kJ.mol-1, in the gas phase and PCM model, respectively.
La ←⎯
⎯

⎯⎯
→ Lb and La ←⎯
Difference of the computed Eas for the La ←⎯
⎯ ⎯⎯
→ Lc pathways can be
⎯

attributed to the inductive effect of the methyl substitution.

In the Ld species, both of the H1 and H2 protons are bonded to the azomethine nitrogens.

⎯⎯
→ Ld and Lc ←⎯
The Lb ←⎯
⎯ ⎯⎯
→ Ld tautomerisms are passed through the TSLb-Ld and
⎯

TSLc-Ld, respectively, the Eas of which are 14.02 and 13.30 kJ.mol-1 in the gas phase, and

8.42 and 6.71 kJ.mol-1, in the PCM model, respectively.

Hence, from kinetical point of view, tautomerization of La to Ld may be progressed in

⎯⎯
→ Lb ←⎯
the both pathways: the La ←⎯
⎯ ⎯⎯
→ Ld or the La ←⎯
⎯ ⎯⎯
→ Lc ←⎯
⎯ ⎯⎯
→ Ld.
⎯

8
Figure 2. The B3LYP optimized geometries of the TSLa-Lb, TSLb-Ld, TSLa-Lc and TSLc-Ld.

9
3.2. Geometry optimization

The elemental analysis results for the titled Schiff base (Anal. Calcd. for C20H20N2O4: C,

70.39; H, 6.16; N, 7.14. Found: C, 67.68; H, 4.89; N, 8.28 %) confirm the proposed formula.

The titled Schiff base has four tautomers, the most stable of which is the OHOH form (La

tautomer). Optimized geometry of the La with labeling of its atoms is shown in Fig. 1.

Selected-structural parameters of this tautomer are listed in Table 1. The calculated-

structural parameters are in agreement with the data reported for the similar compounds [7-

14,22-28].

The calculated-bond lengths are in the expected range [29]. All of three benzene rings are

essentially planar, but each of them lies in a separate plane. The two side-benzene rings

make a dihedral angle of approximately 20° with each other. In the diamine-bridge region,

the middle-benzene ring has a dihedral angle of about 60° with the side benzene rings.

Table 1. Selected structural parameters of the La tautomer.

Bond Bond length (Å) Angle (°) Dihedral angle (°)

O1-H1 1.00 H1-O1-C1 107.1 H1-O1-C1-C2 0.2

H1-N1 1.71 O1-H1-N1 148.5 C1-C2-C3-C4 -0.1

N1-O1 2.62 O1-C1-C2 118.6 C2-C3-O3-H4 179.9

O2-H2 1.00 C1-C2-C3 119.8 C2-C3-C4-H5 -179.9

H2-N2 1.70 C2-C3-O3 117.0 O1-C1-C6-C7 0.2

C1-O1 1.35 O1-C1-C6 121.1 C5-C6-C7-N1 179.7

C1-C2 1.39 C1-C6-C7 121.6 C6-C7-N1-C15 179.1

O3-H4 0.97 C6-C7-N1 122.2 C7-N1-C15-C16 -64.83

10
C2-H3 1.08 C7-N1-C15 120.9 C20-C15-C16-C21 176.2

C4-C5 1.38 N1-C15-C16 122.1 C15-C16-C17-C18 -0.7

C6-C7 1.45 C15-C16-C21 122.5 C18-C19-C20-H18 178.1

C7-H7 1.09 C16-C17-C18 122.5 C1-O1-O2-C8 -40.1

C7-N1 1.29 C3-O3-H4 110.2 C4-C1-C8-C11 -32.2

N1-C15 1.42 C19-N2-C14 121.4 C16-C19-C27-C24 162.8

C15-C16 1.41 N2-C14-H12 121.4 C7-N1-N2-C14 -37.8

C16-C21 1.51 N2-C14- C13 122.0 C2-C1-C9-C8 126.3

C16-C17 1.40 C14- C13-C8 121.6 O1-N1-N2-O2 -13.9

C17-C18 1.39 C13-C8-O2 121.1 C3-C1-C8-C9 -12.8

C18-C19 1.40 C8-O2-H2 106.9 C1-C6-C13-C8 23.4

C19-N2 1.41 O2-H2…N2 148.8 C2-C5-C12-C9 24.1

C14-N2 1.29 O1-H1…N1 148.5 C2-C5-C20-C17 125.9

C14-C13 1.45 C14- C13-C12 120.3 C1-C6-C15-C16 -66.4

C13-C8 1.42 C15- C20-H18 119.3 C8-C13-C19-C18 -147.8

C8-O2 1.35 C18-C19- C20-H18 178.1

O2-H2 1.00

N1-N2 4.80

O1-O2 7.76

N2-C19 1.41

C17-H16 1.09

C20-H18 1.08

11
 The resorcinol OH groups are in the same plane with the aromatic rings (Table 1). The H1

and H2 atoms are engaged in intramolecular-hydrogen bonds with the azomethine nitrogens,

N1 and N2 atoms, respectively. The calculated N…H and N-O distances are 1.71 and 2.621

Å, respectively. These H-bond interactions decrease electron density of the O1-H1 and O2-

H2 bonds. So that the O1-H1 and O2-H2 bonds are longer than the O3-H4 and O4-H9 ones

by 3.2 pm.

The C7=N1 and C14=N2 bonds are in the same plane with the corresponding resorcinol.

Both of the C15-N1 and C19-N2 bond lengths are appropriate size for the C-N single bond,

while both of the C7-N1 and C14-N2 bonds are corresponding to the C=N double bond. As

expected, the methyl substitution is in the same plane with the benzene ring. The calculated

structural parameters are in agreement with the previously reported data for the similar

Schiff bases and their complexes [7-14,22-28].

3.3. NMR spectra

The DFT and experimental 1H- and 13

C-NMR chemical shifts (δ) of the La species are

gathered in Table 2, where the atoms are numbered as in Fig. 1. Good agreement between

the calculated and experimental chemical shifts confirms suitability of the optimized

geometry for the La tautomer as the most stable form of the L.

The H4 and H9 hydrogens are only exceptions, where the experimental chemical shifts

are significantly higher than the calculated ones. These atoms may be engaged in the

intermolecular-hydrogen bonds. In addition, the calculated chemical shifts are corresponding

to the isolated molecule in the gas phase, while the experimental data are from DMSO

solutions. Obviously, the solvent molecules interact with the -OH protons.

A broad signal at 13.60-13.80 ppm is assiged to the H1 and H2 phenolic protons. Their

12
engagement in the intramolecular H-bond (O-H…N), shifts their signals upfield [7-14,30].

13
 1 13
Table 2. Experimental and DFT computed H- and C-NMR chemical shifts of 3,3'-Dihydroxy-4,4'-[5-methyl-1,3-
phenylenebis(nitrilomethylidyne)]-bis-phenol in DMSO solution, δ [ppm].
1 13
H NMR C NMR
Atom Atom
Atom position Exp. Theo. Exp. Theo. Exp. Theo. Atom position Exp. Theo.
position position
H2 13.75 H3 6.81 C1 163.8 173.33 C16 131.8 130.92
13.60-13.80
H1 13.24 H8 6.69 C8 163.8 172.09 C20 129.8 125.02
6.30-6.50
H4 10.33 4.05 H5 5.98 C7 163.4 170.72 C13 119.1 119.27
H9 10.33 3.93 H10 5.83 C3 163.4 168.00 C6 112.4 117.87
H12 8.80 8.85 H14 2.30 2.37 C10 163.4 167.56 C15 110.6 115.58
H7 8.80 8.85 H13 2.30 2.22 C14 163.4 165.05 C4 108.2 107.66
H16 7.33 H15 2.30 1.93 C15 162.5 158.04 C11 108.2 107.66
H18 7.17 C19 162.5 154.70 C2 102.7 107.47
7.30-7.50
H6 7.06 C5 147.9 138.23 C9 102.7 107.38
H11 7.06 C12 147.4 138.23 C21 17.4 19.00
H17 6.91 C17 134.9 137.05

14
3.4. Vibrational spectroscopy
Nowadays, theoretical assignment of the spectra provides a quantitative framework for

understanding and identification of the chemical compounds [7-14,31-33].

Here, the vibrational modes of the La tautomer were analyzed by comparing the DFT and

experimental IR spectra. Assignment of the selected-vibrational frequencies is gathered in

Table 3. The obtained results could be useful in identification of similar compounds.

A broad bond in the 3430-2600 cm-1 spectral region is attributed to overlapping of the O-

H and C-H stretching vibrations [7-14,34,35]. Deconvolution of this region is given in Table

3. The most intensive band is related to the stretching vibrations of the O1-H1 and O2-H2

bonds. Due to the engagement of the H1 and H2 in intramolecular-hydrogen bonds, the O1-

H1 and O2-H2 stretching vibrations have lower energies than the corresponding vibrations

for the O3-H4 and O4-H9 bonds.

The very intensive band in the 1660-1500 cm-1 region is related to the azomethine C=N

bonds. Also, the C-O stretching vibrations result in strong bands at 1223 cm-1 (Table 3) [7-

14,34,35].

Table 3. Selected experimental and calculated IR vibrational frequencies (cm-1) of the 3,3'-
Dihydroxy-4,4'-[5-methyl-1,3-phenylenebis(nitrilomethylidyne)]-bis-phenol.

Experimental Calculated Vibrational assignment

787(m) 813 δop(O1-H1, O2-H2)
840 (s) 880 δop(C20-H18)
976 (m) 950 Breathing of benzene rings
1114 (s) 1099 δip(aromatic hydrogens)
1188(s) 1211 υ(C6-C7, C13-C14, C15-N1, C25-N2)

1223(vs) 1276 υ(C-O)

1342 (m) 1331 δip(C7-H7, C14-H12)

1432 δsci(methyl)

15
 1496 (s) 1481 υ(C-O)+υasym(C=C) benzene rings
1512 (s) 1524 υsym(C=C) bridging benzene ring
1597(vs) 1543-1584 υsym(C=C) benzene rings
1594 υ(C7=N1, C14=N2)
1630(vs)
1601 υ(C=N)+ υsym(C=C) benzene ring of resorcinol
2912 υsym(C-H) methyl
2929 υ(O2-H2, C14-H12)
2941 υ(O1-H1, C7-H7)
2950 υ(O2-H2, C14-H12)
3430-2600 (br)
2960,2987 υasym(C-H) methyl
3041-3067 υ(C-H) aromatic
3076 υ(C2-H3, C9-H8)
3661 υ(O3-H4, O4-H9)
Abbreviations: op, out-of-plane; ip, in-plane; m, medium; s, strong; vs, very strong; br, broad.

3.5. Electrostatic potential map

The electrostatic potentials, VS(r), of the La, Lb, Lc and Ld are shown in Fig. 3, with the

negative potential shown in red and the positive shown in blue. As shown in Fig. 3, there is a

region of positive VS(r) in the most external part of H2 (the region located at the

continuation of O2…H2) in all the structures, but the negative VS(r) is located at the

outermost part of N2. Negative potential around the N2 atom of the La is very prominent

that shows the occurrence of IPT between O2 and N2 [36]. The interaction between the

negative VS(r) region of N2 and the positive VS(r) region of H2 is one of the reasons for

intramolecular hydrogen bond formation of La.

16
 Figure 3. Electrostatic potential map of the La, Lb, Lc, Ld and TsLa-Lb.

3.6. Topological analysis

The Bader theory is a very applicable tool for analyzing hydrogen bonding. Analysis of

the properties of BCPs has often been used for the assessment of the nature of hydrogen

bonds [37-39]. The parameters derived from the Bader theory, as an example of the

Laplacian of the electron density , the electron energy density HC [the sum of the kinetic

electron energy density (GC) and the potential electron energy density (VC)], and -GC/VC,

indicate the type of interaction. For a negative value of a Laplacian, there is no doubt that

interaction or bond formation could be covalency. If and HC are positive, the interaction

is noncovalent. If is positive but HC is negative, and the -GC/VC is smaller than 1, then

the interaction may be classified as partly covalent in nature [36,40].

The topological parameters, such as BCP, , GC, VC, and HC at the BCP of N…HO

17
bond are listed in Table 4. Also, the molecular graphs are shown in Fig. 4.

Table 4: Topological properties at the BCP of N…HO bond and NH…O in La, Lb, Lc, Ld,
TsLa-Lb, TsLa-Lc, TsLa-Ld, TsLb-Ld, TsLc-Ld.

O–H BCP Atom ρ ∇2ρ GC VC HC -GC/VC

La 49 O2-H2 0.321112 -2.18513 0.069836 -0.68596 -0.61612 0.101808
Lb 35 O2-H2 0.043893 0.136244 0.03682 -0.03958 -0.00276 0.930268
Lc 49 O2-H2 0.32231 -2.19936 0.069555 -0.68895 -0.6194 0.100958
Ld 39 O2-H2 0.044601 0.137359 0.037404 -0.04047 -0.00306 0.924286
TsLaLb 36 O2-H2 0.159305 -0.13626 0.092652 -0.21937 -0.12672 0.422355
TsLaLc 40 O2-H2 0.044504 0.137235 0.037336 -0.04036 -0.00303 0.925006
TsLaLd 49 O1-H1 0.322144 -2.1968 0.069642 -0.68848 -0.61884 0.101153
TsLbld 42 O2-H2 0.154596 -0.10075 0.117069 -0.20895 -0.09188 0.56027
TsLcLd 22 O8 - H2 0.156884 -0.11844 0.121908 -0.21421 -0.09230 0.569113
N–H BCP Atom ρ ∇2ρ GC VC HC -GC/VC
La 35 N2-H2 0.054195 0.110972 0.039531 -0.05132 -0.01179 0.770315
Lb 37 N2-H2 0.316307 -1.67904 0.046912 -0.51358 -0.46667 0.091342
Lc 37 N2-H2 0.053352 0.111288 0.039072 -0.05032 -0.01125 0.776424
Ld 37 N2-H2 0.315597 -1.67556 0.046979 -0.51285 -0.46587 0.091604
TsLaLb 23 N2-H2 0.17829 -0.34574 0.069648 -0.22573 -0.15608 0.308546
TsLaLc 34 N2-H2 0.316043 -1.67849 0.046995 -0.51361 -0.46662 0.091499
TsLaLd 27 N1-H1 0.053451 0.111123 0.039101 -0.05042 -0.01132 0.77549
TsLbld 24 N1-H2 0.182953 -0.38112 0.164592 -0.23391 -0.06931 0.70367
TsLcLd 16 N2-H2 0.180715 -0.365 0.160762 -0.23027 -0.06951 0.698134

The molecular graph shows the existence of a BCP between the H2 and N2 atoms, which

are linked by two bond paths. The topological structure indicates that the intramolecular

hydrogen bond existed in La. Table 4 shows that at the BCP of the hydrogen bond, the is

positive, while HC is negative, and the ratio of GC and VC, -GC/VC, is between 0.5 and 1;

all of the topological parameters showed that the intramolecular hydrogen bond, is partly

covalent in nature [41].

The BCP at the BCP increased, which means that the hydrogen bond was stronger than

that in La. Compared with the La tautomer, in the Lb and Lc ones, the absolute values of

, GC, VC, and HC increased, while –GC/VC decreased, which means that the covalent

portion increased in the Lb and Lc tautomers.

18
3.7. AIM analysis on the RCP

The RCP is a point of minimum electron density within the ring surface and a maximum

on the ring line [42]. Table 5 gives the electron density RCP at the RCP and it’s of the

ring (H–O–C=C–C–N), which created by the hydrogen bond formation. The distance

between the RCP and the BCP of the hydrogen bond is also listed in Table 5.

The extended dRCP BCP also prophesied that the hydrogen bond becomes stronger in the Lb

tautomer. This as well means that the properties of RCP: RCP and could probably be

treated as measures of the intramolecular hydrogen bond strength.

Table 5. The topological properties at the RCP, the distance between RCP and BCP in La,
Lb, Lc, Ld, TsLa-Lb, TsLa-Lc, TsLa-Ld.

RCP dRCP BCP

La 0.018444 0.11645 0.829353

Lb 0.016959 0.108571 0.822264
Lc 0.017043 0.109327 0.823856
Ld 0.018339 0.115713 0.827736
TSLa-Lb 0.023235 0.158086 0.939767
TSLa-Lc 0.017033 0.109211 0.823176
TSLa-Ld 0.018359 0.115808 0.82775
TSLc-Ld 0.023209 0.158041 0.927735
TSLb-Ld 0.023221 0.158083 0.926849

19
20
Figure 4. The QTAIM molecular graph of the La, Lb, Lc, Ld, TsLa-Lb, TsLb-Ld, TsLa-
Lc, TsLc-Ld and TsLa-Ld (small green spheres, small red squares, and lines represent
BCP, RCP, and bond paths, respectively)

4. Conclusion

Here, the 3,3'-Dihydroxy-4,4'-[5-methyl-1,3-phenylenebis(nitrilomethylidyne)]-bis-phenol

has been synthesized and characterized experimentally. The newly synthesized species was

investigated computationally by using the DFT methods. Geometries of the four possible

tautomers of the L were fully optimized in the gas phase and methanolic solution using the

PCM model. In both of the gas phase and PCM model, the La is the most stable tautomer of

the L.

In all tautomers, the L has no planar structure. The H1 and H2 phenolic protons are

engaged in the intramolecular hydrogen bond (_O-H…N), which affects considerably their

NMR chemical shifts and energy of their O-H stretching vibration in the IR spectra, too.

This intramolecular hydrogen bonds increase stability of the investigated Schiff base.

Its tautomerization could be occurred in two different pathways. In competition IPTs

between two sites of the La, proton transferring between O2 and N2 could be occurred in

lower barrier energy than the O1 to N1 pathway, which is confirmed by the Electrostatic

21
potential maps of the structures and Topological parameters by AIMall package.

The computed parameters are in good agreement with the values reported for the similar

compounds. On the other hand, the DFT calculated IR frequencies and NMR chemical shifts

also confirm the experimental data, showing validity of the optimized geometries for the

investigated species.

Acknowledgement

We gratefully acknowledge financial support of this investigation by Iran National

Science Foundation, INSF (Project Number 87020068).

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27
Graphical abstract

28
Highlights

 A new ONNO tetradentate Schiff base has been synthesized and characterized
experimentally and theoretically, too.
 Geometries of its tautomers were optimized.
 Theoretical assignments of the IR and NMR spectra have been computed.
 Its tautomerism was demonstrated by kinetical and AIM analysis.

29