Experimental and computational studies on the absorption properties of novel formazan derivatives

Article abstract of DOI:10.3906/kim-1701-50

Eight novel 3-(4-(benzyloxy)phenyl)-5-(4-bromophenyl)-1-(4-substituted-phenyl)formazan (4a-4h) were synthesized by coupling of substituted phenylhydrazones with diazonium salts of 4-bromoaniline. The substituted phenyl-hydrazones, which are intermediate p

Full text of DOI:10.3906/kim-1701-50

Turk J Chem
2017) 41: 710 – 727
Turkish Journal of Chemistry
(
http://journals.tubitak.gov.tr/chem/
¨
˙
⃝
c TUBITAK
Research Article
doi:10.3906/kim-1701-50
Experimental and computational studies on the absorption properties of novel
formazan derivatives
1
,∗
2,3
¨
˘
G u¨ l ¸s en TURKOGLU , M. Emin C¸ INAR
Department of Chemistry, Faculty of Science, Anadolu University, Eski ¸s ehir, Turkey
1
2
˙
˙
Department of Chemistry, Faculty of Arts and Sciences, Istanbul Technical University, Istanbul, Turkey
3
Department Chemie-Biologie, OC1, University Siegen, Siegen, Germany
Received: 20.01.2017
•
Accepted/Published Online: 12.04.2017
•
Final Version: 10.11.2017
Abstract: Eight novel 3-(4-(benzyloxy)phenyl)-5-(4-bromophenyl)-1-(4-substituted-phenyl)formazan (4a–4h) were syn-
thesized by coupling of substituted phenylhydrazones with diazonium salts of 4-bromoaniline. The substituted phenyl-
hydrazones, which are intermediate products, were obtained from the condensation of substituted phenylhydrazines with
1
13
4
-(benzyloxy)benzaldehyde. All target compounds were characterized by using FTIR, H NMR, C NMR, LC−MS
spectrometry, and elemental analysis. Absorption spectra of these compounds in solvents with different polarities were
investigated thoroughly. Time-dependent density functional theory (TD-DFT) studies were conducted to shed light on
their electronic structures, Kohn–Sham orbitals, and electronic transitions.
Key words: Formazans, UV-visible absorption spectroscopy, substituent effect, solvent effect, density functional theory
(
DFT)
1. Introduction
Although the first synthesis of formazans was accomplished over a century ago, they still attract the interest of
1
chemists, biologists, technologists, and other specialists. The conjugated double bonds in the formazan skeleton
(
−NH−N=C−N=N−) render colorful compounds. The tetrazolium/formazan couple is known as a proton
acceptor or oxidant in a special redox system, which is now broadly applied in different areas of biological science,
i.e. medicine, pharmacology, immunology, and botany, particularly in biochemistry and histochemistry.2
These compounds have been investigated comprehensively owing to their ready accessibilities, diverse
chemical reactivities, and broad spectrum of biological activities.3 Moreover, they have been found to possess
important applications. Their important biological applications, such as antiviral, antimicrobial, antiinflamma-
tory, antifungal, antitubercular, anticancer, antiparkinsonian, antifertility, and anticonvulsant, pave the way for
their applications.4
−7
Catalytic, optical and electrochemical properties of metal and boron formazan complexes were compre-
hensively investigated for their applications as functional materials.8
−16
In addition, a new formazan derivative
was introduced for the modification of pencil graphite electrode to determine the paracetamol in electrochemical
sensor applications.17 As a calculation tool for electronic structural properties, molecular modelling techniques
allow a solution for the interpretation of experimental data. Tautomerism, structural and intramolecular hy-
drogen bonding properties of formazan derivatives were widely investigated by means of DFT.1
8−21
∗
Correspondence: gulsent@anadolu.edu.tr
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Herein, new 3-(4-(benzyloxy) phenyl)-5-(4-bromophenyl)-1-(4-substituted-phenyl) formazans (4a–4h)
were synthesized by coupling reactions of substituted phenylhydrazones with appropriate aryl diazonium chlo-
rides in pyridine. Their structures were characterized using elemental analysis, FTIR, 1 H NMR, 13 C NMR,
and LC−MS spectroscopic methods. The substituent effect on their absorption spectra was explored. The
structure and absorption spectra properties of the formazan derivatives were investigated experimentally and
computationally.
2
2
. Results and discussion
.1. Synthesis
The substituted phenylhydrazones (2a–2h) used as the initial substances were obtained in good to excellent
yields (72%–97%) via condensation reactions of substituted phenylhydrazines with 4-(benzyloxy) benzaldehyde.
In intermediate products, 2a,22 2f 23 and 2h24 are known and 2b, 2c, 2e, and 2g are commercially available
materials. Compound 2d also is a novel diarylhyrdazone. Compounds 2a–2h were characterized using FTIR,
1
H NMR, 13 C NMR, and elemental analysis.
The synthesis of formazan derivatives is a well-known transformation and various protocols have been
published.25,26 In the present study, formazans (4a–4h) were synthesized according to the first method reported
by Nineham,27 namely the coupling of substituted phenylhydrazones with 4-bromoaniline diazonium cation (3)
in basic media at 0 C as demonstrated in Scheme 1.28
◦
R
H
O
N
NH2 NH
NH
R
CH OH
3
+
O
o
6
0 C, 2 h
-
H O
2
O
1a-1h
2
a-2h
R
R
_
Cl N2
Br
HN
a = H,
c = 4-Cl,
e = 4-F,
b= 4-OCH3
d= 4-Br
f = 4-NO2
N
3
2
a-2h
N
N
Pyridine, NaOH
-5 °C, 6h
H+
g = 3,4-(CH3)2 h= 2,4-(NO2)2
0
Br
-
O
4
a-4h
Scheme 1. Synthetic route of formazan derivatives.
New formazans 4a–4h, recrystallized from methanol, were obtained in overall yields of 50%–75%. The
optimum basic medium for the coupling step was found to be pH ≥ 12, while the product was formed as a
sticky material that clung to the stirring bar at pH ≤ 9 leaving the reaction incomplete. Moreover, the steric
effects of the substituents located at the aryl aldehydes of the starting material significantly affect the coupling
reactions. Therefore, para-substituted phenyl was chosen to eliminate the steric effects. The analytical and
spectral data fully support the structures of all compounds.
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2.2. Characterization
In the FTIR spectra of formazans 4a–4h, sharp characteristic C=N tension vibration bands are observed
−
1
28−30
between 1593 and 1610 cm , pointing out the existence of chelate form (Scheme 2). The stretching
−
1
frequencies of the N−H groups were observed as a broad band at 3061–3087 cm
for compounds 4a–4g due
28,31,32
1
5
to very strong intramolecular hydrogen bonds (Ph −NH••••N−Ph ) of formazans. However, the N−H
due to nonintramolecular hydrogen bonds. A band
−
1
stretching band for compound 4h appeared at 3276 cm
−
1
recorded at around 1238–1259 cm
in all spectra was attributed to the C−O−C stretching vibration. The
1
−
observation of strong bands at 1456–1498 cm
with the reported FTIR values.2,28,33
demonstrates the −N=N− group, which is in good agreement
1
1
N
N
H
N
N
H
N
5
N
5
3
N 3
N
Br
O
Br
O
Scheme 2. Intramolecular hydrogen bonding and tautomerization of the formazan 4a.
The 1 H NMR data and the calculated coupling constants for formazans 4a–4h are given in the experi-
mental section. Due to the existence of intramolecular hydrogen bonds inside the molecule, characteristic NH
protons of compounds 4a–4g are observed as a singlet in the downfield from 14.31 to 15.06 ppm.6,33,34 However,
weakening of the intramolecular hydrogen bonds was detected most probably from the electronic effect of the
attached NO2 group, pointing out the upfield shift of NH proton (4h, 10.78 ppm).5,7,8,28 The observation of
1
5
these results confirms the pseudoaromatic Ph −NH ··· N−Ph intramolecular hydrogen bond in the formazan
skeleton (Scheme 2). The chemical shifts of the aromatic protons are recorded between 8.25 and 6.31 ppm as
expected. While aliphatic –OCH2− groups’ protons are observed as singlets between 4.36 and 5.15 ppm as
expected, methoxy group protons for compound 4b and methyl group protons (−CH3) for compound 4g are
detected in the upfield at 3.90, 2.36, and 2.33 ppm, respectively.
In the 13 C NMR spectra of formazans 4a–4h, the obtained peaks belonging to carbon atoms in character-
istic N−C=N units are recorded downfield between 164.32 and 158.70 ppm, which are in good alignment with
the reported values.2
8,30,35
While aliphatic −OCH2− carbon atoms are observed in the range of 68.79–70.10
ppm as expected, the methoxy group (−OCH3) for 4b and methyl groups attached to 4g appear at 55.66 and
9.82–19.94 ppm, respectively. H NMR and C NMR spectra confirm the structures given in Scheme 1.
1
13
1
The mass spectra data of 4a–4h are given in the experimental section. In the mass spectrum of the
compound 4a (C26 H21 BrN4 O, M = 484.08 g/mol) the molecular ion peak is observed to be MS, ESI+ :
+
+
+
m/z = 484.1 (27%, M ), 483.1 (100%, M – H ) and 485.1 (94%, M + H ) as anticipated. All synthesized
compounds were evaluated in the same manner and the results obtained from the mass spectra prove the validity
of the structures given in Scheme 1.
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2.3. Absorption spectra
The UV-Vis studies of 4a–4h were performed in solvents with 15 different polarities and the results are listed
in Table 1. The UV-Vis spectra of 4a are given in Figure 1. The visible band in formazans emerges from π–π*
1
,28,34,36
transition of the tautomerizing conjugated formazan skeleton (−NH−N=C−N=N−).
Table 1. UV-vis absorption λmax values of formazans (4a–4h) in various solvents.
a
Comp. DMSO
DMF
(logε)
EtOH
(logε)
MeOH
(logε)
Acetone
(logε)
Dioxane
(logε)
EtOAc
(logε)
CHCl
(logε)
3
b
(
logε)
4
4
4
a
b
c
507 (4.69) 504 (4.70) 505 (4.71) 503 (4.71) 504 (4.94) 513 (4.74)
03 302 300 304
502 (4.74) 503 (4.62) 510 (4.69) 493 (4.83) 503 (4.99) 518 (4.79)
02 304 307 306 307
519 (4.30) 514 (4.80) 520 (4.38) 513 (4.34) 521 (4.40) 531 (4.59)
49 347
10
517 (4.46) 511 (4.64) 522 (4.46) 509 (4.32) 516 (4.46) 532 (4.54)
51 346 347
09
501 (4.65) 501 (4.69) 507 (4.67) 498 (4.72) 502 (4.62) 519 (4.62)
00 291 302 301 304
485 (4.76) 475 (4.48) 499 (4.55) 490 (4.45) 498 (4.78) 514 (4.82)
505 (4.64) 508 (4.51)
302 283
507 (4.85) 516 (4.78)
305 308
527 (4.34) 527 (4.46)
3
3
3
347
305
3
310
4
d
522 (4.38) 531 (4.45)
3
345
303
3
309
4
4
e
f
506 (4.71) 501 (4.60)
300 295
501 (4.94) 501 (4.86)
3
3
72
364
362
364
363
365
372
3
11
316
314
310
4
4
g
504 (4.61) 501 (4.67) 503 (4.27) 499 (4.30) 500 (4.97) 512 (4.67)
84 301 304 305 307
402 (4.98) 396 (5.01) 389 (4.30) 390 (4.32) 388 (5.06) 383 (5.03)
Butanol Propanol DCM Toluene
(logε) (logε) (logε)
505 (4.71) 504 (4.65)
304 306
383 (4.96) 387 (4.98)
2
h
Comp. THF
logε)
Cyclohexane n-Hexane
(
(logε)
(
logε)
514 (4.74) 512 (4.71) 511 (4.76) 508 (4.64) 527 (4.72) 523 (4.65)
04 302 301 300 304 303
516 (4.79) 513 (4.83) 508 (4.82) 510 (4.80) 526 (4.86) 518 (4.74)
07 307 306 306 307 304
531 (4.41) 531 (4.41) 521 (4.26) 525 (4.20) 537 (4.45) 533 (4.34)
08 308 310 276 308 304
530 (4.45) 524 (4.54) 531 (4.32) 531 (4.51) 539 (4.58) 540 (4.36)
12 310 310 304 310 307
516 (4.68) 514 (4.61) 511 (4.69) 514 (4.56) 528 (4.71) 532 (4.68)
02 302 302 299 302 303
508 (4.78) 506 (4.20) 500 (4.08) 507 (4.88) 525 (4.72) 514 (4.11)
(logε)
4
4
4
4
4
4
a
b
c
d
e
f
518 (4.40)
275
3
520 (4.48)
271
3
532 (4.23)
275
3
536 (4.49)
306
3
524 (4.41)
299
3
508 (3.90)
357
3
65
360
365
364
366
307
3
16
310
283
4
4
g
513 (4.80) 510 (4.67) 510 (4.40) 501 (4.78) 526 (4.68) 523 (4.25)
07 307 304 306 308 304
386 (4.99) 392 (4.40) 385 (4.12) 387 (4.97) 383 (5.06) 361 (4.20)
514 (4.70)
304
3
h
375 (4.00)
a
Polarity indexes of solvents: Dimethyl sulfoxide (DMSO): 7.2; N,N-Dimethylformamide (DMF): 6.4; Ethanol (EtOH):
.2; Methanol (MeOH): 5.1; Acetone: 5.1; 1,4-dioxane (Dioxane): 4.8; Ethyl acetate (EtOAc): 4.4; Chloroform (CHCl ):
.1; Tetrahydrofuran (THF): 4.0; n-Butyl alcohol (Butanol): 3.9; Isopropyl Alcohol (Propanol): 3.9; Dichloromethane
5
4
3
b
−1
−1
(
DCM): 3.1; Toluene: 2.4; Cyclohexane: 0.2; n-Hexane: 0.1. Molar absorptivity (logε, 1 M cm ) for the longest
wavelength (π–π*).
Similar π–π* transitions were noted in the case of 4a–4g at λmax 1 of 475–540 nm in different polarity
solvents, indicating the existence of a chelate form due to the inner-molecular hydrogen transfer over a six-
membered ring (Scheme 2).28,30,37,38 Contrary to the other compounds, 4h (λmax 1 = 361−402 nm) shows the
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TURKOGLU and C¸ INAR/Turk J Chem
Figure 1. Electronic absorption bands of compound 4a in various solvents.
1
blue shift arisen from the hydrogen bond between oxygen of the ortho −NO2 group and Ph −NH equilibrium
structure, which hinders the formation of chelation of formazan (Scheme 3).3
7,38
Scheme 3. Hydrogen bond between the ortho-NO
2
and N–H and NH· · · N=N groups in compound 4h.
1
.91 Å
1
.90 Å
Scheme 4. (Left) The relative Gibbs free energies of tautomers at PBE1PBE/6-31G(d) level (relative energies including
−
1
zpe are given in kcal mol ). (Right) Two intramolecular hydrogen bonds in 4h1 significantly stabilize the tautomer
form 1.
The second band λmax 2 between 271 and 372 nm is attributed to the π–π* transitions within the
hydrogen bond chelate ring formed by the azo and hydrazo groups in tautomerization (Scheme 2).37 In
accordance to the values in the literature, the observed λmax 2 of 271–307 nm for 4a, 4b, 4e, and 4g with
inner-molecular hydrogen bonds belongs to the π–π* electronic transitions in the formazan skeleton. The band
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at 341–372 nm for 4c, 4d, and 4f in some solvents arises from an intramolecular charge transfer from solute–
solvent interaction in the form of hydrogen bonding or bulk solvent properties. The observation of these values
1
confirms the intramolecular hydrogen transfer via a pseudoaromatic six-membered ring between Ph −NH with
5
28
N−Ph .
2.3.1. Effect of solvent on the absorption spectra
As depicted in Table 1 and Figure 1, while the polarity of the solvents increases, the absorption peaks of
formazans 4a–4g exhibit a blue shift (λmax = 0–31 nm). However, they have a slight red shift between
1
and 8 nm in toluene and cyclohexane compared to n-hexane, indicating a negative solvatochromism that
points out the more stabilized ground state in a solvent cage of already partly oriented solvent molecules with
stronger polarity. With increasing polarity of the solvents from n-hexane to DMSO, the absorption peaks of the
compound 4h exhibit a red shift (λmax = 8–23 nm). This can be mainly attributed to the stabilization of π and
π* orbitals through solvation by polar solvents.32 According to this result, the compound 4h was demonstrated
to have positive solvatochromism with a decrease in π–π* transition energy concerning the intramolecular
charge transfer (ICT) band within the whole molecule.28,39 While 4d holds the longest absorption wavelength
appearing at 540 nm in cyclohexane, the highest hypsochromic shift having an absorption maximum of 361 nm
was observed for 4h. These results indicate that there is either a hydrogen-bonding interaction between the
solute and solvent molecules or intramolecular charge transfer within the whole molecule.
2.3.2. Effect of substituent on the absorption spectra
The substituent effects on characteristic absorption bands (λmax 1) of formazans 4a−4h were examined in
three solvents (ethanol, THF, and n-hexane) (Table 2). The chemical shift values (∆λmax) were determined
according to the difference between the λmax 1 value of unsubstituted parent compound 4a and λmax 1 values of
substituted formazans (4b–4h).28,37,38 The UV-vis spectra of 4a–4h are given in Figure 2 in ethanol solution.
Table 2. λmax 1 values of 4a–4h and chemical shift (∆λmax) values in EtOH, THF, and n-hexane.
opt
EtOH
THF
n-Hexane
E
g
λmax 1 ∆λa
λmax 1 ∆λa
λmax 1 ∆λa
(EtOH)
(eV)
1.99
2.00
1.94
1.96
1.97
1.97
1.96
b
Comp. Substituent
max
max
max
(
nm)
(nm)
-
(nm)
514
516
531
530
516
508
513
386
(nm)
-
(nm)
518
520
532
536
524
508
514
375
(nm)
-
-2
-14
-18
-6
10
4
4
4
4
4
4
4
4
4
a
b
c
d
e
f
p-H
p-OCH3
p-Cl
p-Br
p-F
505
510
520
522
507
499
-5
-15
-17
-2
6
-2
-17
-16
-2
6
p-NO2
g
h
m, p-(CH3)2 503
o, p-(NO2)2 389
2
116
1
128
143
2.47
a
b
∆
λ
max = λmax 1 (unsubstituted formazan 4a)- λmax 1 (substituted formazan (4b-4h).
Optical band gap,
E
g
= 1240/λonset
.
As shown in Table 2, the absorption value (λmax 1) of compound 4b possessing an electron donating
OCH3 subunit at the para-position is recorded ∆λmax = 5 nm longer wavelength than the parent molecule
a in ethanol. In both –Cl and –Br substituted compounds 4c and 4d, the ∆λmax values showed pronounced
bathochromic shifts of 15 nm and 17 nm, respectively. Under these circumstances, the –Cl and –Br atoms, with
–
4
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Figure 2. Electronic absorption bands of 4a–4h in ethanol.
inductive electron withdrawing and resonance electron donating effects, ended up with two opposite effects.
It can be seen that resonance electron effects are noticeable. The high electronegativity of the fluorine atom
attached to the 1-phenyl ring results in slight bathochromic shifts (∆λmax = 2 nm for 4e, relative to 4a for
the spectra in ethanol and THF). Compound 4f, which includes the para–NO2 group on the 1-phenyl ring
with its strong electron withdrawing effect, had a small shift towards shorter wavelength (∆λmax = 6 nm)
compared to 4a. The λmax 1 value of the compound 4g substituted by the –CH3 group, which is an inductive
electron donating unit at meta- and para-positions, exhibits a small hypsochromic shift (∆λmax = 2 nm). The
λmax 1 value of the compound 4h with strong electron attractive –NO2 groups at ortho- and para-positions
shows a strong hypsochromic shift of ∆λmax = 116 nm compared to 4a. This phenomenon can be attributed
to the formation of a possible hydrogen bond between N–H proton with oxygen of a –NO2 group attached to
the ortho-position of the 1-phenyl ring (Scheme 3). Hence, the electron attractive quality of the –NO2 group
decreases, resulting in disappearance of the resonance effect.28,37,38 Based on these results, electron donating
groups and halogens acting with resonance electron effects generally lead to bathochromic shifts, whereas the
electron withdrawing units result in hypsochromic shifts.
2.4. Computation
The electronic and structural properties of compounds were explored further by conducting density functional
theory (DFT) calculations. Geometry optimizations of both tautomers of formazans were achieved without any
symmetry constraints by means of the Gaussian 09 package program. PBE1PBE40 method with 6-31G(d) ba-
sis set was applied because of its good performance in exploring structures and properties of formazans.20,41,42
Analysis of the harmonic vibrational frequencies using analytical second derivatives was performed to confirm
the minima. Orbital composition analysis with Mulliken partition was carried out using the Multiwfn program
(
a multifunctional wavefunction analyzer).43 TD–DFT calculations with incorporation of solvent effect using a
polarizable continuum model (PCM)44 were carried out using coulomb-attenuating method density functional
theory (CAM–TD–B3LYP)45 with 6-311+G(d,p) basis set to ascertain the lowest singlet–singlet vertical excita-
tions due to the fact that CAM−B3LYP/6-311+G(d,p) provided good results that are close to experimentally
recorded excitation energies.21 Dimethyl sulfoxide, which possesses the highest dielectric constant (ε = 46.83)
among the solvents used in UV-vis measurements, was chosen for TD-DFT calculations. Absorption bands were
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gathered for singlets with NStates of 50. Visualization of MOs with an isosurface value of 0.03 au was done
using GaussView 5.0 and absorption spectra with oscillator strengths were pictured with GaussSum 3.0.46
Relative Gibbs free energies of tautomers calculated at PBE1PBE/6-31G(d) level are given in Scheme
4
(left), which pointed out almost degenerate (∆∆G < 1.0 kcal mol 1) tautomers except for 4b, 4f, and
−
−
1
4h. While tautomer 2 is more stable by 1.56 kcal mol
in the case of 4b, holding MeO substituent at the
para-position of the phenyl unit located on N1, 4f and 4h possessing one and two NO2 subunits, respectively,
−
1
were predicted to have adapted to tautomer form 1 with relative energies of 1.89 kcal mol
−
for 4f and
1
6
.01 kcal mol
for 4h. The reason for the strong shift of the equilibrium towards the tautomer 1 in 4h is
the intramolecular hydrogen bonding formed between N1–H and oxygen of ortho-NO2 unit in a six membered
ring (Scheme 4, right). The DFT calculations illustrated that all molecules are almost planar except for phenyl
◦
groups of benzyloxy substituents, which deviate from planarity by ca. 30 , and para-substituted phenyl unit
◦
located on C3 having a dihedral of 8–12 with core unit. N–H and N· · · H distances were estimated to be 1.02–
˚
˚
1
.03 A and 1.80–1.82 A in both tautomers, respectively, indicating hydrogen in a six-membered heterocyclic
˚
system. However, N· · ·H distance in 4h1 was predicted to be larger (1.90 A) owing to the hydrogen bonding
formed with oxygen of the ortho-NO2 group in a six membered ring (Scheme 4, right).
Frontier molecular orbitals (FMOs) were surfaced to analyze the intramolecular charge transfer (ICT)
properties of formazans (Figure 3). HOMOs of the molecules are spreading over the core unit (–NH–N=C–
N=N–) and phenyl subgroups located on N1 and C3 in tatutomer 1, whereas HOMOs of tautomer 2 were found
to localize on the core unit and phenyl subgroups located on N5 and C3. On the other hand, the localized
LUMOs were obtained on the core unit of the molecules spreading a little over the phenyl substituent attached
on N5. LUMOs of tautomer 2 were observed on a core unit with a contribution of the phenyl group on N1. FMOs
noticeably indicated an efficient ICT from phenyl groups on N1 and C3 to the phenyl unit on N5 over a core
unit in tautomer 1, and from phenyl groups on C3 and N5 to the phenyl unit on N1 via a core unit in tautomer
2. Orbital composition analysis provided the highest HOMO and LUMO orbital compositions of 14.3%–15.4%
for N1 and 19.9%–20.3% for N4 of 4a–4h in tautomer 1, while those were predicted as 14.8%–16.3% for N5
and 20.2%–21.6% for N1 in tautomer 2, respectively. However, NO2 containing 4f and 4h had HOMO orbital
compositions of 14.4% and 13.0% for N1 and LUMO compositions of 20.0% and 19.4% for N5 of 4f and 4h
in tautomer 1, while those were predicted as 12.9% and 10.3% for N5 in HOMO and 17.8% and 16.3% for N2
in LUMO in tautomer 2, respectively. The estimated HOMO energy levels were found to be in the range of
–5.16 to –5.47 eV, whereas those of 4f and 4h possessing one and two NO2 units, respectively, were predicted
as –5.70 to –6.06 eV owing to the strong electron withdrawing groups, which diminish the HOMO energy levels.
A similar phenomenon was observed with LUMO energy levels. While LUMOs have energies between –2.40
and –2.74 eV, those of 4f and 4h with NO2 units were calculated to be –3.08 to –3.59 eV depending on the
number of NO2 units attached on the phenyl group on N1.
The predicted UV-Vis absorption spectra of the less energy tautomers and their vertical excitation
energies are listed in Figure S17 (see Supplementary Information) and Table 3, respectively. The calculated
absorption properties are in good alignment with the experimentally recorded data except for 4h1, having a
predicted absorption band at 486 nm red shifted by 84 nm compared to the experimental value. The reason might
be TD-DFT calculations performed on a gas phase optimized 4h1 with two NO2 units, which can significantly
interact with surrounding solvent and consequently distort the planarity of molecule and hence conjugation is
decreased. The λmax values emerge from HOMO to LUMO excitations, indicating the low energy transitions
taking place from HOMO→LUMO.
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4a1
4a2
4b1
4b2
LUMO (-2.60 eV)
LUMO (-2.58 eV)
LUMO (-2.49 eV) LUMO (-2.40 eV)
HOMO (-5.36 eV)
c1
HOMO (-5.37 eV)
4c2
HOMO (-5.16 eV) HOMO (-5.23 eV)
4d
4
LUMO (-2.74 eV)
LUMO (-2.74 eV)
LUMO (-2.74 eV)
HOMO (-5.46 eV)
HOMO (-5.47 eV)
HOMO (-5.46 eV)
Figure 3. HOMO and LUMO representations of both tautomers of 4a–4d at PBE1PBE/6-31G(d) level (isosurface
value: 0.3 a.u.).
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TURKOGLU and C¸ INAR/Turk J Chem
4e1
4e2
4f1
4f2
LUMO (-2.65 eV)
LUMO (-2.62 eV)
LUMO (-3.08 eV)
LUMO (-3.22 eV)
HOMO (-5.39 eV)
g1
HOMO (-5.41 eV)
4g2
HOMO (-5.78 eV)
4h1
HOMO (-5.70 eV)
4h2
4
LUMO (-2.53 eV)
LUMO (-2.47 eV)
LUMO (-3.26 eV)
LUMO (-3.59 eV)
HOMO (-5.25 eV)
HOMO (-5.29 eV)
HOMO (-6.06 eV)
HOMO (-5.83 eV)
Figure 3. Continued.
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TURKOGLU and C¸ INAR/Turk J Chem
Table 3. Excited state electronic transitions at (PCM:DMSO)-CAM-TD-B3LYP/6-311+G(d,p)//PBE1PBE/6-31G(d)
level.
b
λabs (nm)
E (eV)
2.52
3.92
Fa
0.572
0.521
Major contribution (%)
H → L (96%)
Exp. (nm)
507
−
4
a1 491
16
3
H-1 → L (83%)
−
4
4
4
4
4
b2 482
25
c2 492
17
493
19
e2 484
13
497
2.57
3.81
2.52
3.90
2.51
3.88
2.56
3.96
2.50
3.72
3.78
2.57
3.88
4.33
2.55
3.63
0.660
0.652
0.619
0.516
0.639
0.529
0.590
0.468
0.746
0.388
0.683
0.627
0.505
0.508
0.662
0.783
H → L (96%)
502
302
519
−
3
H-1 → L (89%)
H → L (96%)
3
H-1 → L (76%), H-4 → L (15%)
d
H → L (96%)
517
351
501
300
485
−
3
H-1 → L (79%)
H → L (97%)
3
H-1 → L (74%), H-4 → L (18%)
f
H → L (93%)
3
3
33
28
H → L+1 (70%), H-1 → L (18%)
H-1 → L (62%), H → L+1 (14%)
−
4
g2 482
H → L (96%)
504
−
3
2
20
86
H-1 → L (55%), H → L+1 (36%)
H → L+1 (35%), H-2 → L (26%)
284
402
−
4
h1 486
H → L (91%)
3
42
H-1 → L (80%)
a
b
Oscillator strength. H: HOMO, L: LUMO.
3. Conclusion
In this work, the formazans 4a–4h were prepared in a two-step synthesis in good yields (50%–75%). The
structures of the formazans were characterized by spectroscopic methods. Intramolecular hydrogen bonding
and the effect of para substituents were elaborated by performing DFT calculations. Spectroscopic and
1
5
computational investigations indicated the existence of a hydrogen bond between Ph –NH and N–Ph , which
is in good agreement with the literature. Their optical investigations were performed in different polarity
solvents. The UV-vis measurements indicated that λmax values depend on the solvent polarities. All compounds,
excluding 4h, which shows a batchochromic shift, have a slight hypsochromic shift with increase in the polarity
of solvents. However, unlike 4h, compounds 4a–4g showed negative solvatochromism in polar solvents. The
examination of the substituent effects in various solvents pointed out a bathochromic shift for electron donating
and halogen groups and a hypsochromic shift for electron withdrawing units. The TD-DFT method with
incorporation of solvent (DMSO) was applied to calculate the electronic excitations of formazans, which pointed
out the low energy transitions taking place from HOMO→LUMO. These structural isomers might be promising
candidates as ligands for the coordination chemistry in the field of functional materials.
4
4
. Experimental
.1. Materials and methods
4-Bromoaniline, substituted phenylhydrazines, 4-(benzyloxy) benzaldehyde, NaOH, and high grade organic
solvents for UV-Vis and fluorescence measurements were purchased from Sigma-Aldrich and used without any
further purification. Thin layer chromatography plates (DC-Alufolien Kieselgel 60 F254) were obtained from
Merck (Darmstadt, Germany). Isolation of compounds was performed by using column chromatography over
Sigma silica gel 60 (63–200 µm).
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Microanalyses were carried out using a Leco CHNS-932 elemental analyzer. The melting points were
measured on a Gallenkamp apparatus using a capillary tube. 1 H NMR and 13 C NMR spectra were recorded
on a Bruker DPX FT-NMR (500 MHz) spectrometer (SiMe4 as internal standard) and chemical shifts (δ)
are given in ppm. The spectrometer was equipped with a 5-mm PABBO BB-inverse gradient probe. The
concentration of the solute compounds was 5 mg in 1.0 mL of DMSO-d6 and 10 mg in 1.0 mL of CDCl3 . The
FTIR spectra were recorded as KBr pellets using a Bruker IFS 66 v/S FTIR Spectrophotometer in a 4000–400
−
1
cm
range at room temperature. The electronic spectra of the formazans in different solvents were measured
using a Shimadzu UV–3150 UV–VIS–NIR spectrophotometer. LC–MS studies of the formazans were carried
out with an Agilent 1100 Series LC/MSD Trap VL&SL using atmospheric pressure chemical ionization and
electrospray with positive and negative ion detection.
4.2. Synthesis of substituted phenylhydrazones (2a–2h)
The substituted phenylhydrazones were synthesized by condensation of 4-(benzyloxy) benzaldehyde with
substituted phenylhydrazine compounds.28
4.2.1. General procedure for synthesis of (E)-1-(4-(benzyloxy)benzylidene)-2-phenylhydrazine
(
2a)
To a solution of 2.15 g of 4-(benzyloxy)benzaldehyde (10.2 mmol) in 25 mL of methanol was added a solution
◦
of 1.11 g of phenylhydrazine (920 µL, 10.2 mmol) in 25 mL of methanol dropwise at 60 C. The reaction
mixture was stirred for 2 h and cooled down to room temperature over 30 min. The yellow precipitate was
◦
filtered off and dried in an oven at 60 C. The crude product was recrystallized from methanol. The compound
2a was obtained as bright cream color needles in 97% yield (5.82 g); Rf : 0.69 (n-hexane/ethylacetate, 5:1).
◦
mp: 144–145 C. FTIR (KBr): νmax 3315, 1313 (N–H str., C–N str.), 3033, 1506 (aromatic ring, C–H str.,
C=C str.), 1597 (HC=N str. in Schiff base), 1290, 1259 (C–O–C) cm . 1 H NMR (500 MHz, CDCl3): δ 7.60
−1
(
(
s, 1H); 7.57 (d,J = 8.50 Hz, 2H); 7.46 (s, 1H); 7.38 (t, J = 7.00 Hz, 2H); 7.32 (d, J = 8.00 Hz, 2H); 7.20
d, J = 8.50 Hz, 2H); 7.02 (d, J = 8.00 Hz, 2H); 6.90–6.95 (m, 4H); 5.10 (s, 2H). 13 C NMR (126 MHz,
CDCl3): δ 156.98; 132.95; 136.36; 129.52; 128.47; 127.36; 116.78; 114.16; 70.12. Anal. Calcd. for C20 H18 N2 O
(
302.14): C, 79.44; H, 6.00; N, 9.26. Found: C, 79.20; H, 6.21; N, 9.39.
The other compounds (2b–2h) were prepared in a similar manner.
4.2.2. (E)-1-(4-(Benzyloxy)benzylidene)-2-(4-methoxyphenyl)hydrazine (2b)
◦
Light yellow solid (crystallized from methanol). Yield: 3.11 g (74%); mp: 156–158 C. Rf : 0.59 (n-
hexane/ethylacetate, 5:1). FTIR (KBr): νmax 3300, 1315 (N–H str., C–N str.), 3035, 1525, 1508 (aromatic
−
1
1
ring, C–H str., C=C str.), 1604 (HC=N str. in Schiff base), 1244, (C–O–C) cm
.
H NMR (500 MHz,
CDCl3): δ 7.60 (s, 1H); 7.50 (d,J = 7.50 Hz, 2H); 7.44 (s, 1H); 7.40 (d, J = 8.00 Hz, 2H); 7.35 (t, J = 7.50
Hz, 2H); 7.30 (d, J = 8.00 Hz, 2H); 7.20 (d, J = 7.50 Hz, 1H); 6.96–7.02 (m, 4H); 5.13 (s, 2H); 3.82 (s, 3H).
1
3
C NMR (126 MHz, CDCl3): δ 158.20; 138.00; 132.00; 128.61; 128.05; 127.66; 127.66; 115.15; 114.29; 70.06;
5.45. Anal. Calcd. for C21 H20 N2 O2 (332.15): C, 75.88; H, 6.06; N, 8.43. Found: C, 75.65; H, 6.10; N, 8.20.
5
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TURKOGLU and C¸ INAR/Turk J Chem
4.2.3. (E)-1-(4-(Benzyloxy)benzylidene)-2-(4-chlorophenyl)hydrazine (2c)
◦
Light white needles (crystallized from methanol). Yield: 2.45 g (73%); mp: 154–155 C. Rf : 0.56 (n-
hexane/ethylacetate, 5:1). FTIR (KBr): νmax 3315, 1307 (N–H str., C–N str.), 3033, 1498 (aromatic ring,
−
1
1
C–H str., C=C str.), 1597 (HC=N str. in Schiff base), 1288, 1244 (C–O–C) cm
.
H NMR (500 MHz,
CDCl3): δ 7.64 (s, 1H); 7.58 (d,J = 8.00 Hz, 2H); 7.48 (s, 1H); 7.44 (d, J = 7.50 Hz, 2H); 7.39 (t, J = 7.50
Hz, 2H); 7.34 (d, J = 7.00 Hz, 1H); 7.21 (d, J = 9.00 Hz, 2H); 6.96–7.03 (m, 4H); 5.09 (s, 2H). 13 C NMR (126
MHz, CDCl3): δ 159.20; 137.91; 129.12; 128.60; 128.04; 127.64; 127.46; 115.07; 113.73; 70.06. Anal. Calcd. for
C20 H17 ClN2 O (336.10): C, 71.32; H, 5.09; N, 8.32. Found: C, 71.12; H, 4.95; N, 8.60.
4.2.4. (E)-1-(4-(Benzyloxy)benzylidene)-2-(4-bromophenyl)hydrazine (2d)
◦
White solid (crystallized from methanol). Yield: 3.68 g (81%); mp: 171–172 C. Rf : 0.63 (n-hexane/ethylacetate,
5:1). FTIR (KBr): νmax 3313, 1307 (N–H str., C–N str.), 3034, 1498 (aromatic ring, C–H str., C=C str.), 1602
−
1
1
(
(
HC=N str. in Schiff base), 1288, 1244 (C–O-C) cm
d,J = 8.50 Hz, 2H); 7.48 (s, 1H); 7.44 (d, J = 7.50 Hz, 2H); 7.39 (t, J = 7.50 Hz, 2H); 7.34 (d, J = 8.50
7.50 Hz, 1H); 6.95–7.01 (m, 4H); 5.09 (s, 2H). 13 C NMR (126 MHz, CDCl3): δ
58.20; 138.00; 132.00; 128.61; 128.05; 127.66; 127.46; 115.08; 114.19; 70.06. Anal. Calcd. for C20 H17 BrN2 O
380.05): C, 63.00; H, 4.49; N, 7.35. Found: C, 62.98; H, 4.32; N, 7.16.
.
H NMR (500 MHz, CDCl3): δ 7.64 (s, 1H); 7.58
Hz, 2H); 7.23 (t, J
=
1
(
4.2.5. (E)-1-(4-(Benzyloxy)benzylidene)-2-(4-fluorophenyl)hydrazine (2e)
◦
White-off solid (from methanol). Yield: 2.40 g (75%); mp: 148–149 C. Rf : 0.62 (n-hexane/ethylacetate, 5:1).
FTIR (KBr): νmax 3319, 1313 (N–H str., C–N str.), 3036, 1525, 1508 (aromatic ring, C–H str., C=C str.), 1607
−
1
1
(
(
HC=N str. in Schiff base), 1257, 1211 (C–O–C) cm
d,J = 8.50 Hz, 2H); 7.47 (s, 1H); 7.43 (d, J = 7.00 Hz, 2H); 7.36 (t, J = 7.00 Hz, 2H); 7.30 (d, J = 8.50
8.50 Hz, 1H); 6.94–6.99 (m, 4H); 5.11 (s, 2H). 13 C NMR (126 MHz, CDCl3): δ
57.20; 136.00; 130.00; 128.54; 128.30; 127.16; 126.76; 116.08; 113.18; 70.09. Anal. Calcd. for C20 H17 FN2 O
320.13): C, 74.98; H, 5.35; N, 8.74. Found: C, 74.70; H, 5.12; N, 8.58.
.
H NMR (500 MHz, CDCl3): δ 7.60 (s, 1H); 7.56
Hz, 2H); 7.24 (d, J
=
1
(
(
E)-1-(4-(Benzyloxy)benzylidene)-2-(4-nitrophenyl)hydrazine (2f)
◦
Light red needles (from methanol). Yield: 2.32 g (83%); mp: 182–184 C. Rf : 0.38 (n-hexane/ethylacetate,
5:1). FTIR (KBr): νmax 3263, 1379 (N–H str., C–N str.), 3045, 1510 (aromatic ring, C–H str., C=C str.), 1616
HC=N str. in Schiff base), 1274, 1245 (C–O–C), 1469, 1292 (–NO2 , N=O str.) cm . 1 H NMR (500 MHz,
CDCl3): δ 7.80 (s, 1H); 7.70 (d,J = 8.50 Hz, 2H); 7.62 (s, 1H); 7.54 (d, J = 7.00 Hz, 2H); 7.42 (t, J = 7.00
Hz, 2H); 7.34 (d, J 8.50 Hz, 2H); 7.22 (d, J C
8.50 Hz, 1H); 6.93–6.99 (m, 4H); 5.14 (s, 2H). 13
−
1
(
=
=
NMR (126 MHz, CDCl3): δ 164.20; 148.00; 136.00; 132.54; 128.87; 128.16; 126.76; 115.08; 114.18; 70.08. Anal.
Calcd. for C20 H17 N3 O3 (347.13): C, 69.15; H, 4.93; N, 12.10. Found: C, 69.35; H, 4.84; N, 12.33.
4.2.6. (E)-1-(4-(Benzyloxy)benzylidene)-2-(3,4-dimethylphenyl)hydrazine (2g)
◦
Light yellow solid (from methanol). Yield: 2.37 g (72%); mp: 136–138 C. Rf : 0.72 (n-hexane/ethylacetate,
5
1
:1). FTIR (KBr): νmax 3328, 1315 (N–H str., C–N str.), 3035, 1504 (aromatic ring, C–H str., C=C str.),
612 (HC=N str. in Schiff base), 1296, 1240 (C–O–C) cm . 1 H NMR (500 MHz, CDCl3): δ 7.60 (s, 1H);
−
1
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TURKOGLU and C¸ INAR/Turk J Chem
7.54 (d,J
=
8.50 Hz, 2H); 7.46 (s, 1H); 7.32 (d, J = 7.50 Hz, 2H); 7.20 (d, J
=
7.50 Hz, 2H); 7.02
(
d,J
=
8.50 Hz, 2H); 6.81–6.86 (m, 4H); 5.04 (s, 2H); 2.28 (s, 3H); 2.23 (s, 3H). 13 C NMR (126 MHz,
CDCl3): δ 157.73; 138.60; 134.71; 130.26; 129.20; 128.21; 127.44; 114.65; 112.16; 70.40; 20.29; 19.09. Anal.
Calcd. for C22 H22 N2 O (330.42): C, 79.97; H, 6.71; N, 8.48. Found: C, 79.74; H, 6.52; N, 8.62.
4.2.7. (E)-1-(4-(Benzyloxy)benzylidene)-2-(2,4-dinitrophenyl)hydrazine (2h)
◦
Light brown powder (from methanol). Yield: 3.77 g (96%); mp: 233–235 C. Rf : 0.75 (n-hexane/ethylacetate,
5:1). FTIR (KBr): νmax 3277, 1328 (N–H str., C–N str.), 3089, 1587 (aromatic ring, C=C str., C–H str.),
−
1
1
1614 (HC=N str. in Schiff base), 1259 (C–O–C), 1452, 1280 (–NO2 , N=O str.) cm
.
H NMR (500 MHz,
CDCl3): δ 8.00 (s, 1H); 8.14 (d,J = 8.60 Hz, 1H); 7.68 (d, J = 8.60 Hz, 2H); 7.52 (d, J = 7.00 Hz, 2H);
.48 (d,J = 7.00 Hz, 2H); 7.36 (d,J = 7.00 Hz, 2H); 6.95–7.01 (m, 4H); 5.17 (s, 2H). 13 C NMR (126
7
MHz, CDCl3): δ 161.52; 152.32; 146.33; 139.50; 129.47; 129.10; 128.29; 127.10; 117.18; 115.04; 70.56. Anal.
Calcd. for C20 H16 N4 O5 (392.11): C, 61.22; H, 4.11; N, 14.28. Found: C, 61.40; H, 3.95; N, 14.34.
4.3. General synthesis of formazans 4a–4h
A 4-bromoaniline diazonium salt (3) solution was obtained first. To a solution of substituted arylamine in 10
◦
mL of HCl(aq) (50%, v/v) was dropped a solution of NaNO2 in 5 mL of water at 0–5 C over 1 h. The reaction
mixture was allowed to stir for another 1 h. Completion of diazotization was checked using starch iodide paper.
o
The diazonium salt of substituted arylamine solution was added dropwise at 0–5 C to a solution of 2a–2h
in pyridine (20 mL) and 20% NaOH (10 mL). The coupling reaction mixture was allowed to stir for another
3
h and then poured into 250 mL of ice-cold water. After stirring for 45–60 min, the product was collected by
filtration, washed with water, and dried. The crude product was crystallized out of methanol.
4.3.1. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-phenylformazan (4a)
Compound 4a was obtained from 2a (1.50 g, 4.96 mmol) and diazonium salt 3 (840 mg, 4.96 mmol) as dark
◦
red powder. Yield: 1.20 g, 50%; Rf : 0.67 (n-hexane/ethylacetate, 5:1); mp: 142–143 C. FTIR (KBr): νmax
3
1
062, 1379 (N–H w., C–N str.), 1512, 3028 (aromatic ring, C=C str., C–H str.), 1596 (C=N str. in Schiff base),
−
498 (N=N of formazans), 1238–1170 (C–O–C) cm . 1 H NMR (500 MHz, CDCl3): δ 15.13 (s, 1H); 8.03 (d,
1
J = 9.00 Hz, 2H); 7.69 (d,J = 7.50 Hz, 2H); 7.54 (d, J = 9.00 Hz, 2H); 7.50 (d, J = 9.00 Hz, 2H);
.46 (dd, J = 8.00, 5.00 Hz, 4H); 7.41 (t, J = 7.50 Hz, 2H); 7.35 (d,J = 7.50 Hz, 1H); 7.33 (t,J = 7.50
Hz, 1H); 7.05 (d,J = 9.00 Hz, 2H); 5.14 (s, 2H). 13 C NMR (126 MHz, CDCl3): δ 158.77; 148.21; 146.53;
7
1
7
41.36; 136.97; 132.42; 130.11; 129.41; 128.70; 128.59; 127.96; 127.47; 127.29; 119.94; 119.67; 119.13; 114.79;
+
+
+
0.06. ESI-MS: m/z485.0 ((M+H) , 94%); 484.1 ((M) , 27%); 483.1 ((M-H) , 100%). Anal. Calcd. for
C26 H21 BrN4 O: C, 64.34; H, 4.36; N, 11.54. Found: C, 64.10; H, 4.42; N, 11.45.
4.3.2. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-(4-methoxyphenyl)formazan (4b)
Compound 4b was obtained from 2b (1.20 g, 3.61 mmol) and diazonium salt 3 (610 mg, 3.61 mmol) as a claret
◦
red solid. Yield: 1.40 g, 75%; Rf : 0.50; mp: 153–155 C. FTIR (KBr): νmax 3064, 1352 (N–H w., C–N str.),
1
1
510, 3004 (aromatic ring, C=C str., C–H str.), 1598 (C=N str. in Schiff base), 1490 (N=N of formazans),
−1
1
243–1172 (C–O–C) cm
.
H NMR (500 MHz, CDCl3): δ 14.77 (s, 1H); 8.02 (d,J = 9.00 Hz, 2H); 7.85
7
23

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TURKOGLU and C¸ INAR/Turk J Chem
(
d,J = 9.00 Hz, 2H); 7.47 (d, J = 7.50 Hz, 2H); 7.44 (d, J = 9.00 Hz, 2H); 7.40 (t, J = 7.50 Hz,
2
H); 7.34 (t, J
s, 2H); 3.90 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 162.15; 158.72; 146.18; 143.29; 141.25; 136.99; 132.25;
30.19; 128.58; 127.95; 127.47; 127.44; 123.71; 116.64; 115.55; 114.72; 114.63; 70.05; 55.66. ESI-MS: m/z515.1
= 7.25 Hz 1H); 7.27 (d, J = 9.00 Hz, 2H); 7.03 (d, J = 8.00, 2.50 Hz, 4H); 5.13
(
1
+
+
+
(
(M+H) , 100%); 514.1 ((M) , 27%); 513.1 ((M–H) , 99%). Anal. Calcd. for C27 H23 BrN4 O2 : C, 62.92; H,
.50; N, 10.87. Found: C, 62.74; H, 4.62; N, 10.66.
4
4.3.3. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-(4-chlorophenyl)formazan (4c)
Compound 4c was obtained from 2c (1.21 g, 3.59 mmol) and diazonium salt 3 (610 mg, 3.59 mmol) as a dark
◦
purple solid. Yield: 1.10 g, 58%; Rf : 0.75; mp: 148–150 C. FTIR (KBr): νmax 3063, 1382 (N–H w., C–N str.),
1
1
596, 3033 (aromatic ring, C=C str., C–H str.), 1602 (C=N str. in Schiff base), 1467 (N=N of formazans),
244–1171 (C–O–C) cm . 1 H NMR (500 MHz, CDCl3): δ 15.04 (s, 1H); 8.01 (d, J = 9.00 Hz, 2H); 7.62
−
1
(
d, J = 7.75 Hz, 2H); 7.56 (dd, J = 9.00, 4.00 Hz, 2H); 7.38–7.45 (m, 4H); 7.20 (d, J = 9.00 Hz, 2H);
.05 (d, J = 9.00 Hz, 1H); 7.01 (d, J = 8.50 Hz, 2H); 6.98 (d, J = 9.00 Hz, 2H); 5.14 (s, 2H). 13 C NMR
7
(
126 MHz, CDCl3): δ 159.32; 158.87; 146.79; 143.54; 137.88; 136.71; 132.49; 129.58; 129.10; 128.60; 128.04;
+
1
5
27.62; 127.46; 127.34; 120.18; 119.79; 115.06; 114.83; 113.71; 70.05. ESI-MS: m/z519.0 ((M+H) , 100%);
+
+
18.0 ((M) , 28%); 517.0 ((M-H) , 100%). Anal. Calcd. for C26 H20 BrClN4 O: C, 60.07; H, 3.88; N, 10.78.
Found: C, 60.38; H, 3.92; N, 10.59.
4.3.4. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-1,5-bis(4-bromophenyl)formazan (4d)
Compound 4d was obtained from 2d (1.43 g, 3.75 mmol) and diazonium salt 3 (640 mg, 3.75 mmol) as a violet
◦
solid. Yield: 1.41 g, 67%; Rf : 0.79; mp: 157–159 C. FTIR (KBr): νmax 3087, 1380 (N–H w., C–N str.), 1593,
3
1
033 (aromatic ring, C=C str., C–H str.), 1605 (C=N str. in Schiff base), 1498 (N=N of formazans), 1247–
−
1
1
172 (C–O–C) cm
.
H NMR (500 MHz, CDCl3): δ 15.02 (s, 1H); 8.00 (d, J = 9.00 Hz, 2H); 7.56 (dd,
J = 9.00, 7.00 Hz, 4H); 7.51 (d, J = 9.00 Hz, 2H); 7.47 (d, J = 7.50 Hz, 1H); 7.43 (dd, J = 7.00, 5.25 Hz,
2
5
1
H); 7.40 (t, J = 7.50 Hz, 2H); 7.33 (d, J = 9.00 Hz, 2H); 7.04 (d, J = 10.00 Hz, 1H); 6.97 (dd, J = 9.00,
.25 Hz, 2H); 5.13 (s, 2H). 13 C NMR (126 MHz, CDCl3): δ 159.33; 158.88; 146.77; 137.96; 132.50; 131.96;
28.60; 128.03; 127.99; 127.64; 127.46; 127.53; 120.81; 120.13; 115.06; 114.83; 114.17; 70.05. ESI-MS: m/z565.0
+
+
+
(
(M+H) , 47%); 564.0 ((M) , 28%); 563.0 ((M-H) , 100%). Anal. Calcd. for C26 H20 Br2 N4 O: C, 55.34; H,
.57; N, 9.93. Found: C, 55.51; H, 3.84; N, 10.04.
3
4.3.5. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-(4-fluorophenyl)formazan (4e)
Compound 4e was obtained from 2e (1.33 g, 4.15 mmol) and diazonium salt 3 (710 mg, 2.65 mmol) as a dark
◦
purple solid. Yield: 1.00 g, 74%; Rf : 0.52; mp: 168–170 C. FTIR (KBr): νmax 3061, 1352 (N–H w., C–N str.),
1
1
589, 3034 (aromatic ring, C=C str., C–H str.), 1603 (C=N str. in Schiff base), 1492 (N=N of formazans),
244–1172 (C–O–C) cm . 1 H NMR (500 MHz, CDCl3): δ 14.96 (s, 1H); 8.00 (d, J = 9.00 Hz, 2H); 7.78
−
1
(
dd, J = 9.00, 5.00 Hz, 2H); 7.48 (dd, J = 8.00, 2.87 Hz, 4H); 7.41 (d, J = 7.50 Hz, 2H); 7.38 (dd,
7.00, 2.87 Hz, 2H); 7.34 (t, J 7.50 Hz, 1H); 7.18 (t, J 8.50 Hz, 2H); 7.04 (d, J 9.00
Hz, 2H); 5.13 (s, 2H). 13 C NMR (126 MHz, CDCl3): δ 164.32; 162.32; 158.82; 146.76; 146.74; 144.50; 141.31;
J
=
=
=
=
136.94; 132.39; 129.93; 128.59; 128.98; 127.47; 127.32; 122.38; 122.31; 118.14; 117.96; 116.50; 116.32; 114.79;
724

¨
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TURKOGLU and C¸ INAR/Turk J Chem
+
+
+
7
0.06. ESI-MS: m/z503.0 ((M+H) , 88%); 502.1 ((M) , 27%); 501.1 ((M-H) , 100%). Anal. Calcd. for
C26 H20 BrFN4 O: C, 62.04; H, 4.00; N, 11.13. Found: C, 62.16; H, 4.28; N, 11.32.
4.3.6. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-(4-nitrophenyl)formazan (4f)
Compound 4f was obtained from 2f (1.22 g, 3.51 mmol) and diazonium salt 3 (600 mg, 3.51 mmol) as a darkish
◦
solid. Yield: 1.10 g, 59%; Rf : 0.58; mp: 209 C. FTIR (KBr): νmax 3083, 1321 (N–H w, C–N str.), 1502,
3031 (aromatic ring, C=C str., C–H str.), 1593 (C=N str. in Schiff base), 1477 (N=N of formazans), 1245–1171
C–O–C) cm . 1 H NMR (500 MHz, CDCl3): δ 14.31 (s, 1H); 8.25 (d, J = 8.50 Hz, 2H); 8.01 (d, J = 8.50
−
1
(
Hz, 2H); 7.80 (d, J = 8.50 Hz, 2H); 7.70 (d, J = 8.50 Hz, 2H); 7.41–7.46 (m, 6H); 7.35 (d, J = 7.00
Hz, 1H); 7.07 (d, J = 8.50, Hz, 2H); 5.15 (s, 2H). 13 C NMR (126 MHz, CDCl3): δ 159.49; 150.88; 148.92;
143.23; 142.75; 136.74; 132.85; 128.64; 128.17; 128.07; 127.47; 126.80; 125.86; 123.81; 114.93; 114.39; 70.10.
+
+
ESI-MS: m/z529.0 ((M) , 40%); 528.0 ((M–H) , 100%). Anal. Calcd. for C26 H20 BrN5 O3 : C, 58.88; H,
.80; N, 13.20. Found: C, 58.77; H, 3.68; N, 13.31.
3
4.3.7. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-(3,4-dimethylphenyl)formazan (4g)
Compound 4g was obtained from 2g (1.00 g, 3.02 mmol) and diazonium salt 3 (510 mg, 3.02 mmol) as a dark
◦
purple solid. Yield: 0.90 g, 58%; Rf : 0.71; mp: 177–179 C. FTIR (KBr): νmax 3062, 1386 (N–H w., C–N str.),
1
1
2
7
587, 3033 (aromatic ring, C=C str., C–H str.), 1604 (C=N str. in Schiff base), 1490 (N=N of formazans),
244–1190 (C–O–C) cm . 1 H NMR (500 MHz, DMSO-d6): δ 15.06 (s, 1H); 8.03 (dd, J = 7.00, 2.00 Hz,
H); 7.56 (s, 1H); 7.53 (dd, J = 8.00, 2.00 Hz, 1H); 7.48 (t, J = 7.25 Hz, 3H); 7.41 (d, J = 7.50 Hz, 2H);
.38 (d, J = 9.00 Hz, 2H); 7.34 (t, J = 7.50 Hz, 1H); 7.24 (d, J = 8.50 Hz, 1H); 7.04 (dd, J = 7.00,
−
1
2
1
1
9
.00 Hz, 2H); 5.14 (s, 2H); 2.36 (s, 3H); 2.33 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 158.70; 148.49; 144.80;
41.24; 139.00; 137.82; 137.01; 132.30; 130.55; 130.27; 128.58; 127.94; 127.47; 127.33; 121.59; 118.32; 118.04;
+
+
+
17.48; 114.75; 70.05; 19.82; 19.94. ESI-MS: m/z513.1 ((M+H) , 100%); 512.1 ((M) , 27%); 511.1 ((M–H) ,
5%). Anal. Calcd. for C28 H25 BrN4 O: C, 65.50; H, 4.91; N, 10.91. Found: C, 65.37; H, 4.77; N, 10.79.
4.3.8. (2Z,4E)-3-(4-(Benzyloxy)phenyl)-5-(4-bromophenyl)-1-(2,4-dinitrophenyl)formazan (4h)
Compound 4h was obtained from 2h (1.71 g, 4.36 mmol) and diazonium salt 3 (740 mg, 4.36 mmol) as a light
◦
claret solid. Yield: 1.3 g, 52%; Rf : 0.63; mp: 214–216 C. FTIR (KBr): νmax 3276, 1328 (N–H w., C–N str.),
1
1
7
6
589, 3032 (aromatic ring, C=C str., C–H str.), 1610 (C=N str. in Schiff base), 1456 (N=N of formazans),
−
1
1
259–1172 (C–O–C) cm
.
H NMR (500 MHz, DMSO-d6): δ 10.78 (s, 1H); 8.04 (d, J = 2.50 Hz, 1H);
.81 (s, 1H); 7.52 (dd, J = 9.50, 2.00 Hz, 1H); 7.25 (d, J = 9.50 Hz, 2H); 6.93 (d, J = 9.00 Hz, 2H);
.65 (d, J = 7.50 Hz, 3H); 6.59 (t, J = 7.50 Hz, 2H); 6.52 (t, J = 7.50 Hz, 1H); 6.31 (d, J = 9.00 Hz,
2
1
H); 4.36 (s, 2H). 13 C NMR (126 MHz, DMSO-d6): δ 159.06; 153.03; 148.23; 145.95; 139.57; 135.53; 133.81;
28.67; 128.06; 127.42; 126.93; 125.49; 124.82; 123.52; 122.09; 115.75; 115.64; 114.38; 114.10; 99.14; 68.79.
−
−
ESI-MS: m/z574.0 ((M) , 35%); 573.0 ((M–H) , 100%). Anal. Calcd. for C26 H19 BrN6 O5 : C, 54.27; H,
.33; N, 14.61. Found: C, 54.32; H, 3.40; N, 14.52.
3
7
25

¨
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TURKOGLU and C¸ INAR/Turk J Chem
Acknowledgments
GT would like to express her deep thanks to Asst Prof Halil Berber, Faculty of Science, Department of Chemistry,
Anadolu University, for his kind advice and valuable help. GT is grateful to Anadolu University Research Council
for its financial support. We are indebted to the High-Performance-Computing (HPC) Linux Cluster HorUS of
the University of Siegen for the computer time provided.
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7
27

Supplementary Information
NMR spectra, computed absorption spectra, and Cartesian coordinates.
NMR spectra of target compounds
1
Figure S1. H NMR (500 MHz, CDCl
3
) spectrum of compound 4a.
1
3
3
Figure S2. C NMR (126 MHz, CDCl ) spectrum of compound 4a.
1

1
3
Figure S3. H NMR (500 MHz, CDCl ) spectrum of compound 4b.
1
3
3
Figure S4. C NMR (126 MHz, CDCl ) spectrum of compound 4b.
2

1
3
Figure S5. H NMR (500 MHz, CDCl ) spectrum of compound 4c.
1
3
3
Figure S6. C NMR (126 MHz, CDCl ) spectrum of compound 4c.
3

1
3
Figure S7. H NMR (500 MHz, CDCl ) spectrum of compound 4d.
1
3
3
Figure S8. C NMR (126 MHz, CDCl ) spectrum of compound 4d.
4

1
3
Figure S9. H NMR (500 MHz, CDCl ) spectrum of compound 4e.
1
3
3
Figure S10. C NMR (126 MHz, CDCl ) spectrum of compound 4e.
5

1
3
Figure S11. H NMR (500 MHz, CDCl ) spectrum of compound 4f.
1
3
3
Figure S12. C NMR (126 MHz, CDCl ) spectrum of compound 4f.
6

1
3
Figure S13. H NMR (500 MHz, CDCl ) spectrum of compound 4g.
1
3
3
Figure S14. C NMR (126 MHz, CDCl ) spectrum of compound 4g.
7

1
6
Figure S15. H NMR (500 MHz, DMSO-d ) spectrum of compound 4h.
1
3
6
Figure S16. C NMR (126 MHz, DMSO-d ) spectrum of compound 4h.
8

Computation
Absorption Spectra
4
a1
4b2
4c2
4
e2
4f1
4
d
4
g2
4h1
Figure S17. Absorption spectra predicted at (PCM:DMSO)-CAM-TD-B3LYP/6-311+G(d,p)//PBE1PBE/6-31G(d)
level.
9

Cartesian Coordinates
4
a1
C
C
C
C
C
C
H
H
1.7642540 -3.3146930 0.1465240
0.4801720 -3.8305430 -0.0649570
-0.5826530 -2.9509070 -0.2695320
-0.3554690 -1.5767230 -0.2571990
0.9192030 -1.0476840 -0.0458950
1.9762970 -1.9495200 0.1557840
2.5822730 -4.0108020 0.3059180
-1.5883840 -3.3170720 -0.4446060
-1.1876580 -0.9010490 -0.4212110
2.9750470 -1.5615670 0.3254760
1.1542980 0.4127000 -0.0398640
2.4094940 0.8092260 -0.0102380
2.7177360 2.0800260 0.0034680
1.9427560 2.7530130 -0.0182120
4.0436320 2.5008180 0.0381040
5.1089480 1.5941890 0.0294100
4.2951780 3.8770440 0.0802060
6.4108800 2.0736660 0.0649210
4.8983970 0.5315540 -0.0079910
5.6037100 4.3402560 0.1148610
3.4633320 4.5777640 0.0881700
6.6693330 3.4433540 0.1079320
7.2359620 1.3665080 0.0574440
5.7899130 5.4101260 0.1482210
7.6920180 3.8075450 0.1349950
0.0120710 1.1873210 -0.0592150
0.1560500 2.4509680 -0.0742550
-1.0438070 3.1806990 -0.0702360
-2.3168580 2.6089080 0.0674800
-0.9241030 4.5679760 -0.2024320
-3.4441720 3.4130170 0.0652460
-2.4000320 1.5336200 0.1810500
-2.0498840 5.3799160 -0.2091650
0.0667930 5.0008420 -0.3066280
-3.3044610 4.7942230 -0.0752490
-4.4330050 2.9795810 0.1745800
-1.9593290 6.4556130 -0.3157260
H
C
H
C
H
H
H
N
N
C
C
C
C
H
C
H
C
H
H
4.8068050 0.4455930 -0.1924000
5.5981440 4.2253560 0.1818910
3.4541160 4.4849370 0.2436650
6.6389000 3.3068200 0.0718830
7.1691000 1.2305180 -0.1536080
5.8129310 5.2852650 0.2844390
7.6702440 3.6482140 0.0862470
-0.0088590 1.1740790 -0.0466190
0.0767670 2.4830210 -0.0536040
-1.0633320 3.2741970 -0.0653290
-2.3493080 2.7225380 -0.0348020
-0.9060850 4.6646820 -0.1067700
-3.4583660 3.5546920 -0.0480670
-2.4624280 1.6452710 0.0024700
-2.0171830 5.4953230 -0.1191080
0.0912790 5.0968400 -0.1322110
-3.2906820 4.9363910 -0.0902580
-4.4575190 3.1321560 -0.0237500
-1.8959490 6.5728870 -0.1519400
Br -4.8936290 5.8678270 -0.0225450
O
C
H
H
C
C
C
C
H
C
H
C
H
H
H
O
C
H
H
H
0.3787660 -5.1827940 -0.0548450
-0.9025030 -5.7593060 -0.1888230
-1.5692310 -5.3601780 0.5923550
-1.3421490 -5.4929270 -1.1613530
-0.7926310 -7.2543520 -0.0599570
0.2122920 -7.8417260 0.7092930
-1.7394860 -8.0712220 -0.6793690
0.2664600 -9.2246650 0.8553240
0.9573260 -7.2084490 1.1804530
-1.6912560 -9.4533430 -0.5258020
-2.5200840 -7.6230210 -1.2912630
-0.6859780 -10.0344930 0.2424220
1.0576020 -9.6714960 1.4518100
-2.4342720 -10.0771860 -1.0155320
-0.6421120 -11.1140970 0.3581870
7.9353070 3.8451700 -0.0610800
8.2388540 5.2198820 -0.0305460
7.8519450 5.6988110 0.8788070
9.3277960 5.2887180 -0.0366510
7.8390990 5.7412390 -0.9105320
H
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
H
N
N
C
C
C
C
H
C
H
C
H
H
Br -4.8066760 6.0625600 -0.1069110
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3992590 -5.1838730 -0.0321460
-0.8702160 -5.7753510 -0.2105190
-1.5682120 -5.3836850 0.5466100
-1.2782000 -5.5145510 -1.1981530
-0.7479020 -7.2690780 -0.0773390
0.2441090 -7.8463930 0.7157440
-1.6719680 -8.0950910 -0.7187780
0.3082190 -9.2288100 0.8633050
0.9714220 -7.2060160 1.2045870
-1.6140020 -9.4765820 -0.5636490
-2.4422700 -7.6545340 -1.3490060
-0.6214770 -10.0478570 0.2282730
1.0892450 -9.6678860 1.4785600
-2.3392320 -10.1076370 -1.0704590
-0.5698960 -11.1269590 0.3453880
4b2
C
C
C
C
C
C
H
H
H
1.7513640 -3.2648500 0.1412680
0.4815270 -3.8133830 -0.0582850
-0.6055550 -2.9608270 -0.2657790
-0.4122530 -1.5839800 -0.2675680
0.8500720 -1.0199990 -0.0654020
1.9302510 -1.8925330 0.1365190
2.5879940 -3.9384630 0.3006700
-1.6022230 -3.3538640 -0.4346480
-1.2602800 -0.9282220 -0.4353000
2.9201300 -1.4800160 0.2955400
1.0402230 0.4472210 -0.0641460
2.3646970 0.8560900 -0.0623540
2.5935410 2.1060190 -0.0654460
0.9660250 2.9144660 -0.0896950
3.9469500 2.4639010 -0.0723890
5.0134520 1.5491210 -0.1417310
4.2303100 3.8298690 -0.0122280
6.3144830 2.0014560 -0.1446920
4.7912290 0.4891790 -0.1977570
5.5394310 4.2956170 -0.0118740
3.4023020 4.5315820 0.0395870
6.5916320 3.3780340 -0.0782050
7.1517910 1.3124910 -0.2005660
5.7279400 5.3620180 0.0389640
-0.0454190 1.1841760 -0.0649910
0.0291140 2.4968360 -0.0806660
-1.1168460 3.2767860 -0.0667240
-2.3971790 2.7143400 0.0005920
-0.9754930 4.6690390 -0.1201070
-3.5141990 3.5359880 0.0111800
-2.4991520 1.6363400 0.0471350
-2.0943970 5.4890770 -0.1083960
0.0165740 5.1108420 -0.1739000
-3.3614370 4.9187830 -0.0434330
-4.5081840 3.1037990 0.0638360
-1.9842180 6.5675610 -0.1505930
H
H
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
4b1
Br -4.8440600 5.8844530 -0.0773430
C
C
C
C
C
C
H
H
H
1.7575780 -3.3046670 0.1172450
0.4734390 -3.8284700 -0.0708880
-0.5974530 -2.9554220 -0.2610830
-0.3777250 -1.5799800 -0.2581360
0.8971370 -1.0426140 -0.0701760
1.9621100 -1.9380030 0.1176080
2.5821990 -3.9954320 0.2657270
-1.6039850 -3.3276510 -0.4180940
-1.2160000 -0.9091490 -0.4110780
2.9615170 -1.5442590 0.2692150
1.1230380 0.4193250 -0.0741200
2.3805260 0.8218510 -0.0717680
2.6780280 2.0923640 -0.0700540
1.8936040 2.7574910 -0.0779850
4.0010550 2.5254680 -0.0673210
5.0781460 1.6290030 -0.0985510
4.2528900 3.8972090 -0.0349270
6.3728570 2.1092230 -0.0948380
4.8790720 0.5638590 -0.1283810
5.5570240 4.3813490 -0.0318630
3.4222770 4.5987930 -0.0091960
6.6285860 3.4869780 -0.0613850
7.2187580 1.4291920 -0.1196470
5.7213990 5.4526960 -0.0055050
-0.0170030 1.1887020 -0.0745510
0.1223230 2.4558000 -0.0952400
-1.0795280 3.1797800 -0.0729130
-2.3487890 2.6029340 0.0807060
-0.9692990 4.5683740 -0.2036320
-3.4797970 3.4019830 0.0955670
-2.4257900 1.5270290 0.1925800
-2.0986200 5.3752330 -0.1927360
0.0179590 5.0064070 -0.3206050
-3.3487610 4.7839540 -0.0432810
-4.4649820 2.9633600 0.2169380
-2.0142130 6.4516080 -0.2979890
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3779700 -5.1836960 -0.0554870
-0.9042020 -5.7535130 -0.2117740
-1.5808140 -5.3534490 0.5602980
-1.3267690 -5.4813750 -1.1901980
-0.8036280 -7.2494860 -0.0865850
0.1860120 -7.8445670 0.6964200
-1.7445340 -8.0592520 -0.7240910
0.2311010 -9.2282880 0.8380070
0.9265440 -7.2168590 1.1819050
-1.7055560 -9.4421390 -0.5749250
-2.5130450 -7.6049050 -1.3466500
-0.7154390 -10.0310490 0.2069480
1.0103980 -9.6812690 1.4453220
-2.4437430 -10.0604980 -1.0786740
-0.6787150 -11.1112670 0.3193070
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
H
H
4
a2
C
C
C
C
C
C
H
H
H
1.7491890 -3.2907540 0.1884980
0.4808680 -3.8294750 -0.0457860
-0.5941140 -2.9684550 -0.2797190
-0.3908400 -1.5930470 -0.2729950
0.8698830 -1.0393410 -0.0362380
1.9382280 -1.9199500 0.1920920
2.5762260 -3.9708920 0.3686730
-1.5887510 -3.3538650 -0.4757070
-1.2297350 -0.9311420 -0.4613850
2.9265630 -1.5153380 0.3791600
1.0711910 0.4259200 -0.0255460
2.3955930 0.8276810 0.0038460
2.6318860 2.0751160 0.0179140
1.0182850 2.8926110 -0.0363600
3.9952630 2.4212900 0.0321350
5.0441990 1.4980420 -0.0824770
4.2806720 3.7847730 0.1585570
6.3558750 1.9454810 -0.0618220
Br -4.8885700 6.0312250 -0.0281680
O
C
H
H
C
C
C
C
H
C
H
C
H
0.4102960 -5.1688280 -0.0396710
-0.8585260 -5.7695380 -0.1869760
-1.5413350 -5.3823570 0.5861890
-1.2921520 -5.5130610 -1.1647930
-0.7219860 -7.2621470 -0.0550790
0.2881800 -7.8304490 0.7215270
-1.6497980 -8.0966220 -0.6798880
0.3663040 -9.2120770 0.8694100
1.0184320 -7.1834070 1.1970870
-1.5776480 -9.4774570 -0.5244870
-2.4343480 -7.6632340 -1.2973750
-0.5671790 -10.0396060 0.2510520
1.1613480 -9.6439280 1.4717110
H
C
N
N
H
C
C
C
C
ꢀ
10
ꢀ

H
H
O
C
H
H
H
-2.3060360 -10.1150720 -1.0184240
-0.5045960 -11.1181220 0.3683140
7.8996560 3.7094350 -0.0870540
8.2387270 5.0772690 -0.0255590
7.8754060 5.5394630 0.9011810
9.3286590 5.1173530 -0.0450180
7.8401930 5.6286010 -0.8867720
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
2.3942630 0.8320080 0.0068970
2.6314910 2.0805700 0.0210810
1.0156610 2.8970590 -0.0338450
3.9940710 2.4210920 0.0319230
5.0405620 1.4945660 -0.0811120
4.2908980 3.7823920 0.1529650
6.3557820 1.9260060 -0.0656050
4.8014120 0.4421730 -0.1867110
5.6068120 4.2227000 0.1727710
3.4727020 4.4918300 0.2377800
6.6325970 3.2884640 0.0632320
7.1726100 1.2171460 -0.1557250
5.8402850 5.2775750 0.2707960
-0.0089030 1.1775040 -0.0412040
0.0752590 2.4852700 -0.0497460
-1.0659250 3.2759940 -0.0621990
-2.3510330 2.7229670 -0.0275230
-0.9092210 4.6661780 -0.1085510
-3.4606310 3.5542700 -0.0417170
-2.4632710 1.6457530 0.0137910
-2.0209150 5.4959930 -0.1217970
0.0877390 5.0990600 -0.1373740
-3.2939450 4.9360670 -0.0889040
-4.4594490 3.1312100 -0.0141740
-1.9006350 6.5735080 -0.1585370
C
H
C
H
H
-2.0521400 5.3797920 -0.2076200
0.0646150 5.0011810 -0.3009810
-3.3069140 4.7937910 -0.0759720
-4.4358270 2.9790200 0.1721130
-1.9616260 6.4554620 -0.3141570
Br -4.8461320 5.8833080 -0.0810600
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3786290 -5.1806350 -0.0486200
-0.9027170 -5.7516050 -0.2120980
-1.5831660 -5.3524430 0.5569760
-1.3200050 -5.4787460 -1.1924880
-0.8012170 -7.2475050 -0.0878760
0.1805930 -7.8420860 0.7053280
-1.7338180 -8.0576650 -0.7369160
0.2262140 -9.2259060 0.8454570
0.9149010 -7.2141480 1.1999240
-1.6944670 -9.4407010 -0.5891110
-2.4959410 -7.6036110 -1.3674680
-0.7121550 -10.0291340 0.2028480
0.9994110 -9.6786170 1.4606840
-2.4260730 -10.0594840 -1.1018200
-0.6750230 -11.1094350 0.3141390
4
c1
C
C
C
C
C
C
H
H
H
1.7642580 -3.3128380 0.1575140
0.4809440 -3.8286610 -0.0602990
-0.5808180 -2.9489670 -0.2709730
-0.3535300 -1.5749310 -0.2586310
0.9203580 -1.0462200 -0.0415090
1.9763890 -1.9478980 0.1666600
2.5811160 -4.0090490 0.3220550
-1.5856350 -3.3152270 -0.4507560
-1.1848570 -0.8994420 -0.4275020
2.9743030 -1.5602300 0.3417990
1.1556670 0.4137690 -0.0364380
2.4091110 0.8115100 -0.0084040
2.7154130 2.0851320 0.0059960
1.9393700 2.7568830 -0.0141070
4.0395490 2.5028250 0.0366520
5.1039830 1.5947430 0.0230380
4.3008340 3.8771380 0.0799860
6.4095190 2.0602850 0.0546890
4.8936480 0.5322820 -0.0154020
5.6076100 4.3415230 0.1110360
3.4764770 4.5859410 0.0920980
6.6593190 3.4302440 0.0988030
7.2390700 1.3607340 0.0435610
5.8114390 5.4065930 0.1455760
0.0107840 1.1878500 -0.0558550
0.1537020 2.4507520 -0.0699370
-1.0462550 3.1805430 -0.0670910
-2.3190290 2.6080290 0.0698620
-0.9262600 4.5676730 -0.1996840
-3.4463390 3.4119060 0.0664390
-2.4021010 1.5328000 0.1839700
-2.0521670 5.3793200 -0.2078090
0.0645150 5.0009040 -0.3033450
-3.3067460 4.7932560 -0.0746310
-4.4351810 2.9784460 0.1752730
-1.9618680 6.4549660 -0.3147980
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
H
H
Br 8.4394270 4.0537440 0.1361440
4e1
C
C
C
C
C
C
H
H
1.7630760 -3.3134450 0.1603000
0.4807780 -3.8298640 -0.0606260
-0.5806310 -2.9506300 -0.2746000
-0.3538600 -1.5764470 -0.2624380
0.9190810 -1.0468900 -0.0420240
1.9746460 -1.9482080 0.1694210
2.5798610 -4.0091700 0.3274300
-1.5848630 -3.3172830 -0.4570250
-1.1848570 -0.9011560 -0.4340060
2.9719690 -1.5601690 0.3471850
1.1533040 0.4134710 -0.0366240
2.4085560 0.8112320 -0.0081340
2.7139600 2.0827700 0.0061630
1.9366280 2.7539360 -0.0138340
4.0402030 2.5029830 0.0367270
5.1048110 1.5947850 0.0180780
4.2981550 3.8778150 0.0848530
6.4106910 2.0610220 0.0498970
4.8928920 0.5328020 -0.0242530
5.6048110 4.3449590 0.1158330
3.4714180 4.5836830 0.1008570
6.6461650 3.4287490 0.0985360
7.2516870 1.3753500 0.0354560
5.8237330 5.4068510 0.1541920
0.0116560 1.1878970 -0.0563610
0.1556470 2.4519670 -0.0698840
-1.0440280 3.1816600 -0.0672340
-2.3170870 2.6094900 0.0692850
-0.9247520 4.5690170 -0.1993710
-3.4446020 3.4132670 0.0659010
-2.4001070 1.5342110 0.1829650
-2.0507440 5.3805810 -0.2073140
0.0659570 5.0025160 -0.3028240
-3.3053280 4.7945470 -0.0745800
-4.4333670 2.9794740 0.1743710
-1.9604240 6.4562880 -0.3139310
Br -4.8103850 6.0606260 -0.1067960
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3990460 -5.1798730 -0.0248260
-0.8687480 -5.7719600 -0.2152510
-1.5738500 -5.3799400 0.5350310
-1.2669500 -5.5115240 -1.2069140
-0.7471810 -7.2655730 -0.0805290
0.2371420 -7.8425020 0.7223270
-1.6647060 -8.0917720 -0.7310490
0.3002350 -9.2249090 0.8704330
0.9594560 -7.2020500 1.2184280
-1.6078710 -9.4732290 -0.5753260
-2.4288680 -7.6514360 -1.3688530
-0.6229490 -10.0441740 0.2262670
1.0753020 -9.6637840 1.4932960
-2.3278860 -10.1045120 -1.0892070
-0.5721680 -11.1232530 0.3438370
H
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
H
H
Cl 8.2830320 3.8243410 0.0815700
4d
C
C
C
C
C
C
H
H
1.7640690 -3.3124310 0.1593640
0.4807610 -3.8282950 -0.0584860
-0.5810900 -2.9486480 -0.2689190
-0.3538800 -1.5746000 -0.2564270
0.9200190 -1.0458700 -0.0394120
1.9761300 -1.9475010 0.1686380
2.5809730 -4.0086220 0.3237460
-1.5859020 -3.3149560 -0.4486300
-1.1852620 -0.8991470 -0.4251510
2.9740360 -1.5597830 0.3436920
1.1554200 0.4140920 -0.0345090
2.4087500 0.8117020 -0.0065900
2.7153780 2.0854510 0.0076130
1.9396530 2.7574790 -0.0125110
4.0394150 2.5026050 0.0372400
5.1033230 1.5936120 0.0242470
4.3010190 3.8771270 0.0787860
6.4089840 2.0591350 0.0544170
4.8924710 0.5311620 -0.0126490
5.6082600 4.3405720 0.1083760
3.4769330 4.5863330 0.0904500
6.6586550 3.4286360 0.0964620
7.2377350 1.3588270 0.0437170
5.8118120 5.4056150 0.1413590
0.0103130 1.1881830 -0.0544140
0.1532690 2.4509860 -0.0684270
-1.0466420 3.1808810 -0.0665310
-2.3196030 2.6084140 0.0688700
-0.9263220 4.5680320 -0.1985540
-3.4468180 3.4124010 0.0645030
-2.4029030 1.5331530 0.1825050
Br -4.8460900 5.8826460 -0.0784180
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3786730 -5.1810180 -0.0501580
-0.9028220 -5.7518180 -0.2129440
-1.5830050 -5.3519920 0.5560220
-1.3203050 -5.4795330 -1.1934130
-0.8016730 -7.2476600 -0.0877200
0.1804950 -7.8419850 0.7052280
-1.7350000 -8.0579920 -0.7355050
0.2257520 -9.2257190 0.8463480
0.9153440 -7.2139190 1.1988560
-1.6960070 -9.4409290 -0.5867070
-2.4974280 -7.6041490 -1.3658410
-0.7133350 -10.0291100 0.2049980
0.9992290 -9.6782320 1.4613700
-2.4281870 -10.0598440 -1.0984360
-0.6764920 -11.1093400 0.3170680
H
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
H
H
Br -4.8450930 5.8841720 -0.0782410
Cl 8.2985170 4.0068250 0.1378730
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3788210 -5.1827580 -0.0501460
-0.9021070 -5.7533550 -0.2152440
-1.5842730 -5.3528310 0.5516590
-1.3175780 -5.4821200 -1.1969190
-0.8017160 -7.2491600 -0.0882440
0.1819300 -7.8432620 0.7030050
-1.7371690 -8.0596990 -0.7327500
0.2265380 -9.2268770 0.8457390
0.9183220 -7.2149880 1.1940300
-1.6987730 -9.4424720 -0.5824040
-2.5008500 -7.6060750 -1.3617390
-0.7146130 -10.0304250 0.2076570
1.0011800 -9.6791640 1.4594800
-2.4326470 -10.0614840 -1.0916050
4
c2
C
C
C
C
C
C
H
H
1.7471930 -3.2872780 0.2067690
0.4810020 -3.8260400 -0.0395140
-0.5913490 -2.9649840 -0.2853690
-0.3877320 -1.5896400 -0.2788500
0.8707750 -1.0361630 -0.0304440
1.9364660 -1.9166260 0.2101440
2.5720610 -3.9673820 0.3965850
-1.5840220 -3.3504660 -0.4907720
-1.2245780 -0.9279870 -0.4770090
2.9231010 -1.5125500 0.4072400
1.0722780 0.4290430 -0.0204530
H
H
C
H
ꢀ
11
ꢀ

H
F
-0.6782740 -11.1105510 0.3209650
7.9094060 3.8743010 0.1286100
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
4.2991690 3.8827890 0.0702590
6.4043970 2.0507780 0.0711150
4.8866220 0.5264700 0.0045760
5.6018360 4.3435140 0.1056220
3.4729070 4.5889290 0.0715720
6.6455580 3.4224300 0.1063040
7.2452780 1.3669000 0.0711780
5.8281720 5.4028570 0.1336760
0.0101690 1.1873080 -0.0578650
0.1510680 2.4468240 -0.0741970
-1.0482270 3.1785340 -0.0698640
-2.3213500 2.6065410 0.0650370
-0.9238590 4.5652940 -0.1999080
-3.4466840 3.4124540 0.0624290
-2.4066410 1.5312690 0.1768820
-2.0481880 5.3789030 -0.2074860
0.0678170 4.9966860 -0.3018880
-3.3038960 4.7943110 -0.0761290
-4.4365750 2.9811870 0.1696390
-1.9561580 6.4545260 -0.3123950
H
H
-4.4630270 3.1421290 -0.0278180
-1.8975430 6.5803930 -0.1676410
Br -4.8067110 6.0705900 -0.1251330
4
e2
O
C
H
H
C
C
C
C
H
C
H
C
H
0.4074560 -5.1706210 -0.0169750
-0.8577870 -5.7663480 -0.2181410
-1.5700880 -5.3737050 0.5248710
-1.2466390 -5.5087160 -1.2141210
-0.7337840 -7.2592610 -0.0792260
0.2389220 -7.8318130 0.7407720
-1.6380100 -8.0890230 -0.7435870
0.3038400 -9.2137700 0.8918680
0.9511740 -7.1887130 1.2479190
-1.5796050 -9.4700700 -0.5847170
-2.3927780 -7.6519690 -1.3946720
-0.6062180 -10.0366980 0.2337880
1.0698850 -9.6494200 1.5279610
-2.2890890 -10.1043520 -1.1093830
-0.5540360 -11.1154210 0.3537680
7.9991470 3.7394670 0.0850710
8.2047020 4.9329850 0.2428660
8.8680150 2.8938040 -0.0599440
C
C
C
C
C
C
H
H
1.7476320 -3.2885520 0.1987640
0.4804350 -3.8268380 -0.0427180
-0.5926850 -2.9653520 -0.2836230
-0.3887400 -1.5900710 -0.2768200
0.8708470 -1.0367930 -0.0330340
1.9372090 -1.9178520 0.2023970
2.5731700 -3.9689850 0.3845610
-1.5862990 -3.3504330 -0.4853070
-1.2261030 -0.9278820 -0.4709240
2.9246960 -1.5140070 0.3954600
1.0723350 0.4285060 -0.0224010
2.3966770 0.8298810 0.0052580
2.6347260 2.0774680 0.0192040
1.0164050 2.8973090 -0.0345700
3.9966120 2.4201990 0.0314640
5.0449630 1.4929390 -0.0709890
4.2897850 3.7839980 0.1437100
6.3594720 1.9260070 -0.0538990
4.8050920 0.4400570 -0.1691950
5.6046040 4.2275780 0.1648880
3.4684400 4.4906330 0.2200570
6.6208180 3.2880090 0.0657070
7.1890280 1.2309260 -0.1350290
5.8526060 5.2798080 0.2550790
-0.0077250 1.1763290 -0.0427190
0.0765610 2.4855390 -0.0504480
-1.0645130 3.2754680 -0.0622260
-2.3496800 2.7221310 -0.0291730
-0.9092490 4.6660630 -0.1062480
-3.4598420 3.5528080 -0.0425910
-2.4613850 1.6448000 0.0102460
-2.0214440 5.4952340 -0.1187110
0.0874180 5.0997590 -0.1337520
-3.2941820 4.9346830 -0.0874090
-4.4583700 3.1289220 -0.0163100
-1.9016910 6.5728960 -0.1535950
H
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
H
H
N
O
O
Br -4.8400880 5.8851440 -0.0790860
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3773410 -5.1757190 -0.0605500
-0.9087200 -5.7470790 -0.1960460
-1.5693680 -5.3504240 0.5911170
-1.3482970 -5.4700180 -1.1651810
-0.8023260 -7.2429990 -0.0803430
0.1743530 -7.8369670 0.7199580
-1.7243400 -8.0538050 -0.7431450
0.2253380 -9.2210750 0.8532380
0.9011230 -7.2086550 1.2253410
-1.6799660 -9.4375170 -0.6018670
-2.4819060 -7.6000930 -1.3793180
-0.7029260 -10.0251970 0.1968710
0.9944090 -9.6734930 1.4737480
-2.4032500 -10.0571200 -1.1251940
-0.6616850 -11.1058460 0.3029270
8.0155700 3.9043360 0.1444090
8.1909500 5.1144520 0.1736740
8.9109130 3.0716920 0.1451460
4g1
C
C
C
C
C
C
H
H
H
1.7639310 -3.3230660 0.1323660
0.4783840 -3.8369850 -0.0737180
-0.5842940 -2.9556590 -0.2713250
-0.3554330 -1.5817490 -0.2571280
0.9207220 -1.0543800 -0.0506390
1.9776500 -1.9579900 0.1436110
2.5820550 -4.0203850 0.2860090
-1.5913290 -3.3201830 -0.4424480
-1.1875090 -0.9045860 -0.4156530
2.9777000 -1.5714730 0.3089140
1.1569600 0.4059270 -0.0415520
2.4145320 0.8004510 -0.0134810
2.7229210 2.0695840 0.0020540
1.9471970 2.7426200 -0.0168450
4.0490010 2.4911170 0.0360680
5.1177020 1.5943800 0.0245000
4.2996420 3.8664890 0.0810060
6.4111570 2.0947350 0.0599430
4.9235100 0.5288270 -0.0148120
5.5982070 4.3636930 0.1162670
3.4614890 4.5612830 0.0911970
6.6817190 3.4644680 0.1060220
0.0182610 1.1820180 -0.0560890
0.1642150 2.4467230 -0.0688520
-1.0345850 3.1773510 -0.0593330
-2.3080380 2.6069190 0.0813540
-0.9146690 4.5650160 -0.1888810
-3.4347310 3.4120660 0.0846290
-2.3918610 1.5314560 0.1927550
-2.0397120 5.3780020 -0.1899530
0.0762910 4.9972030 -0.2955490
-3.2944230 4.7933360 -0.0531830
-4.4235480 2.9791080 0.1962260
-1.9484750 6.4538720 -0.2944630
H
C
N
N
H
C
C
C
C
H
C
H
C
N
N
C
C
C
C
H
C
H
C
H
H
H
H
N
O
O
Br -4.8115760 6.0586960 -0.1042890
4f2
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3981850 -5.1809430 -0.0286970
-0.8705290 -5.7722960 -0.2140530
-1.5725290 -5.3801890 0.5391090
-1.2727920 -5.5115870 -1.2040290
-0.7491290 -7.2660020 -0.0799700
0.2381030 -7.8433550 0.7190200
-1.6694580 -8.0919000 -0.7268980
0.3012540 -9.2257790 0.8669130
0.9625620 -7.2030990 1.2122400
-1.6125230 -9.4733900 -0.5714170
-2.4359480 -7.6512770 -1.3617050
-0.6247270 -10.0447240 0.2263500
1.0785720 -9.6649360 1.4867760
-2.3347740 -10.1043970 -1.0825040
-0.5739040 -11.1238260 0.3437380
7.8915330 3.7020720 0.0813730
C
C
C
C
C
C
H
H
1.7505110 -3.2768330 0.2259970
0.4874450 -3.8178400 -0.0335580
-0.5833370 -2.9586920 -0.2928710
-0.3816950 -1.5830130 -0.2866490
0.8733710 -1.0282680 -0.0253470
1.9378740 -1.9062940 0.2291920
2.5738700 -3.9555020 0.4267680
-1.5730220 -3.3460260 -0.5085720
-1.2177250 -0.9236250 -0.4955850
2.9217450 -1.5010080 0.4378750
1.0741360 0.4366810 -0.0158360
2.3879440 0.8454400 0.0129810
2.6219130 2.0975990 0.0347220
1.0131030 2.9018470 -0.0256430
3.9847800 2.4345960 0.0416900
5.0254190 1.5063020 -0.1231200
4.2823400 3.7931910 0.2103840
6.3402500 1.9340890 -0.1088210
4.7787680 0.4606560 -0.2668930
5.5973380 4.2288170 0.2295430
3.4647280 4.4969250 0.3337720
6.6096770 3.2897840 0.0695590
7.1654670 1.2429920 -0.2360470
5.8539840 5.2728690 0.3642240
-0.0117690 1.1863840 -0.0391280
0.0711990 2.4894870 -0.0468580
-1.0704400 3.2824240 -0.0643280
-2.3554200 2.7298220 -0.0334500
-0.9091590 4.6715690 -0.1117530
-3.4632510 3.5628830 -0.0524760
-2.4693240 1.6527900 0.0088730
-2.0193460 5.5031670 -0.1299590
0.0887410 5.1023030 -0.1378120
-3.2933800 4.9447420 -0.1007910
H
H
C
N
N
H
C
C
C
C
H
C
H
C
H
H
N
N
C
C
C
C
H
C
H
C
H
H
F
Br -4.8333250 5.8853470 -0.0478620
4
f1
O
C
H
H
C
C
C
C
H
C
H
C
H
0.3743710 -5.1904870 -0.0665040
-0.9093430 -5.7576200 -0.2173330
-1.5818650 -5.3572070 0.5581750
-1.3361880 -5.4838490 -1.1934950
-0.8112640 -7.2539310 -0.0938300
0.1821680 -7.8517630 0.6822280
-1.7582250 -8.0612410 -0.7255000
0.2249630 -9.2356690 0.8228410
0.9272860 -7.2258950 1.1630350
-1.7214510 -9.4442940 -0.5773540
-2.5298120 -7.6047650 -1.3426840
-0.7275750 -10.0359350 0.1976830
1.0072200 -9.6907670 1.4247650
-2.4644020 -10.0606710 -1.0765320
-0.6926380 -11.1163000 0.3092840
8.0976750 3.9632210 0.1430130
8.2975770 4.5541950 1.0461550
C
C
C
C
C
C
H
H
1.7704860 -3.3125210 0.1232870
0.4807370 -3.8254440 -0.0670380
-0.5846120 -2.9431990 -0.2489690
-0.3549340 -1.5699100 -0.2355310
0.9251620 -1.0447650 -0.0460230
1.9851130 -1.9487850 0.1333580
2.5894610 -4.0110970 0.2650530
-1.5938020 -3.3074010 -0.4063870
-1.1891960 -0.8929880 -0.3814050
2.9875090 -1.5635530 0.2862820
1.1641740 0.4135010 -0.0405110
2.4131350 0.8105340 -0.0130700
2.7216840 2.0905080 0.0016380
1.9481810 2.7632620 -0.0196130
4.0385650 2.5029980 0.0359290
5.1025560 1.5875240 0.0355340
H
H
C
N
N
H
C
C
H
H
C
H
ꢀ
12
ꢀ