Synthesis, photochromic properties, and complex formation with metal ions of hydrazones based on a spiropyran of oxaindane series

Article abstract of DOI:10.1134/S1070363212080166

A series of hydrazones based on a new spiropyran oxaindane series was synthesized. The compounds were found to possess photochromism and are characterized by a high rate of spontaneous decoloration of their photoinduced merocyanine form. Dark and photoind

Full text of DOI:10.1134/S1070363212080166

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 8, pp. 1432–1437. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.D. Popov, I.A. Shcherbakov, A.O. Bulanov, E.Yu. Shasheva, Yu.N. Tkachenko, O.I. Kobeleva, T.M. Vyalova, V.A. Barachevskii,
2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 8, pp. 1362–1367.
Synthesis, Photochromic Properties,
and Complex Formation with Metal Ions of Hydrazones
Based on a Spiropyran of Oxaindane Series
L. D. Popova, I. A. Shcherbakova, A. O. Bulanova, E. Yu. Shashevaa, Yu. N. Tkachenkoa,
O. I. Kobelevab, T. M. Vyalovab, and V. A. Barachevskiib
a Southern Federal University, ul. B. Sadovaya 105, Rostov-on-Don, 344104 Russia
e-mail: ldpopov@mail.ru
b Center of Photochemistry, Russian Academy of Sciences, Moscow, Russia
e-mail: barva@photonics.ru
Received June 9, 2011
Abstract—A series of hydrazones based on a new spiropyran oxaindane series was synthesized. The com-
pounds were found to possess photochromism and are characterized by a high rate of spontaneous decoloration
of their photoinduced merocyanine form. Dark and photoinduced formation of complex compounds in the
reaction of metal ions with molecules of the hydrazones in solution was observed.
DOI: 10.1134/S1070363212080166
A promising area of application of photochromic
spiro compounds is the development of a reversible
photocontrolled chemosensors [1–4]. In continuation
of our preceeding research in this area [5–7], we
present in this paper the results of spectral and kinetic
studies of photochromism and complexation with
metal ions of a number of newly synthesized hydra-
zones based on spiropyranes of oxaindane series (II–
IX). The synthesis scheme is shown below.
The composition and structure of compounds II–IX
were established on the basis of elemental analysis
1
(Table 1), IR and H NMR spectroscopy. Methods of
synthesis and spectral characteristics of the synthesized
CH3
H3C
O
CH3
H3C
O
3'
O
3
CH3
4'
H3C
4
O
5'
7'
O
6'
5
6
8
ArCONHNH2
OH
N
S
7
O
O
HN
HN
OH
N
O
HN
OH
2
3
4
6
5
R
R
I
II−VIII
IX
R = H (II), CH3 (III), OCH3 (IV), N(CH3)2 (V), F (VI), Br (VII), NO2 (VIII).
1432

SYNTHESIS, PHOTOCHROMIC PROPERTIES, AND COMPLEX FORMATION
Table 1. Yields and elemental analysis data of spiropyrans I–IX
1433
Found, %
H
Calculated, %
H
Yield,
%
mp,
°С
Comp. no.
Formula
С
N
C
N
–
72
62
87
70
74
68
59
72
81
106
150
172
173
165
130
138
180
225
73.85
73.43
73.70
70.90
71.76
70.34
61.73
66.45
68.65
5.50
5.16
5.61
5.25
5.54
4.45
4.34
4.34
5.42
–
С19H16O4
74.01
73.23
73.62
71.04
71.62
70.26
61.79
66.24
68.77
5.23
5.20
5.49
5.30
5.80
4.76
4.19
4.49
5.34
I
6.57
6.45
6.34
8.80
6.40
5.43
8.56
8.78
С26H22N2O4
С27H24N2O4
С27H24N2O5
С28H27N3O4
С26H21FN2O4
С26H21BrN2O4
С26H21N3O6
С27H25N3O3S
6.57
6.36
6.14
8.95
6.30
5.54
8.91
8.91
II
III
IV
V
VI
VII
VIII
IX
compounds are given in the experimental section. The
results of the spectral-kinetic studies of photochromic
properties of synthesized compounds are presented in
Fig. 1 and Table 2.
that the photoinduced moiety of this compound does
not undergo a spontaneous decoloration, but returns to
the original colorless form under the action of visible
light.
Figure 1 shows the photoinduced changes in the
absorption spectra of compound II. The absorption
spectrum of the original form of the compound
consists of several bands with a maximum at 310 nm.
The photoinduced absorption band occupies the region
from 400 to 550 nm. The hydrazone exhibits photo-
chromic properties: after photo-coloration (Fig. 2,
curve 2) spontaneous decoloration occurs of the photo-
induced form (Fig. 2, curve 3). However, the
magnitude of the photoinduced optical density at a
wavelength of the absorption band maximum of the
photoinduced form is insignificant.
The replacement of the carbonyl group in the
substituent of compound II by thiocarbonyl (com-
pound IX) causes a red shift of the absorption bands of
both the initial and photoinduced forms, although
photo-coloration is weak (Table 2).
All investigated compounds are characterized by a
high rate of spontaneous decoloration in comparison
with the nitro-substituted spiropyrans [1], which
largely determines the low photoinduced optical
density under the conditions of steady-state photolysis.
The results of the spectral-kinetic studies of the
synthesized compounds of the class of spiropyran
derivatives indicate their photochromic trans-
The introduction of weak electron-donor
substituents in the para-position of the phenyl ring
(hydrazones III and IV) and electron-acceptor group
(hydrazone VII), in some cases almost does not
change the position and shape of the absorption band
of the initial and photoinduced forms (Table 2). In
other cases at the introduction of electron-donor
(hydrazones IV and V) and electron-acceptor
(hydrazone VI) substituents in the phenyl ring of the
hydrazone fragment of the molecule there is an
increase in the photoinduced changes in optical density
(Table 2, Fig. 2). In these cases the absorption band of
the original moiety undergoes a blue shift, while the
absorption band of the photoinduced moiety suffers a
red shift relative to that of the unsubstituted compound
II (Table 2).
D
λ, nm
The nitro-substituted derivative VIII is charac-
terized by a shift of the absorption band to the spectral
region of longer wavelengths (Fig. 3). It is noteworthy
Fig. 1. The absorption spectra of solution of compound II
in acetonitrile: (1) before iradiation, (2) after irradiation
with UV light through an UVC-1 filter.
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1434
POPOV et al.
Table 2. Spectral and kinetic characteristics of photo-
CH3
H3C
chromic transformations of spiropyran in acetonitrilea
O
Comp. λАmax, nm
DА
λВmax ΔDBphot ΔDBphot/DА kBA, s–1
,
no.
nm
O
310
307
310
333
305
310
0.98
0.85
1.27
1.25
1.13
0.79
450 0.02
450 0.02
453 0.18
445 0.15
467 0.10
438 0.03
0.02
0.02
0.14
0.12
0.09
0.04
0.10
0.03
0.004
0.025
0.038
0.016
0.016
0.038
–
II
III
IV
V
OH
N
HN
VI
VII
VIII
IX
R
X
257/320 0.90/0.70 485 0.08
А
CH3
325 0.93 486 0.03
0.040
H3C
O
a
λAmax and λBmax are the maxima of absorption bands of the initial
and photoinduced forms of photochromic compounds,
respectively; DA is optical density at the maximum of absorption
band of the initial form; ΔDBphot is the photoinduced change in
optical density at the maximum of the absorption band of the
photoinduced forms in the state of photo-equilibrium; kBA is the
spontaneous decoloration constant at 250°C.
hν1
hν2, kT
OH
O
N
HN
X
formations, like those established for the other types of
spiro compounds [1], namely, mutual photoinduced
transformations between spiropyran and merocyanine
forms (A and B, respectively).
B
R
solution in the absence of light. The absorption spectra
of these products shows a structurized absorption band
of the complex with Mg+2 with two pronounced
maxima or La+3, with three maxima.
In the course of study the properties were examined
of all new compounds toward ability of complexation
of the molecules of synthesized hydrazones with metal
cations. Table 3 lists the results of comparative
spectral and kinetic studies.
Similar absorption spectra with minor changes in
the position of the maxima of the absorption bands,
depending on the structure of the compounds, are
observed for the products of interaction of the
carbonyl-containing spiropyran hydrazones molecules
Table 3 shows that all investigated hydrazones react
with metal ions. The introduction of bivalent Mg+2 or
trivalent La+3 ions into the solution of photochromic
hydrazones II and VIII leads to the coloration of the
D
D
λ, nm
λ, nm
Fig. 2. Absorption spectra of solution of compound IV in
acetonitrile: (1) before irradiation, (2–4) after consecutive
irradiation through the filter UVC-1.
Fig. 3. The absorption spectra of solution of compound
VIII: (1) before irradiation, (2–4) after consecutive
irradiation through the filter UVC-1.
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SYNTHESIS, PHOTOCHROMIC PROPERTIES, AND COMPLEX FORMATION
1435
Table 3. The spectral-kinetic characteristics of the complexes of spiropyran with metal ions in acetonitrilea
Comp. no.
Ion
Li+
Ag+
Mg+2
La+3
Li+
Ag+
Mg+2
La+3
Li+
Ag+
Mg+2
La+3
Li+
λАmax, nm
DА
λВmax (ΔDBorig), nm
ΔDBphot
310
310
0.86
1.01
445
500
0.03
II
0.17
320
0.87
450(0.94)/545(1.39)
460(1.00)/540(1.53)
435(0.05)
–
330
0.71
–
305
0.85
0.03
III
IV
V
307
0.86
505
0.33
320
0.75
445(0/82)/540(1.10)
460(0.98)/533(1.27)
440
–
325
0.58
–
310
1.28
0.03
310
1.27
500
0.16
323
1.19
450(1.05)/545(1.46)
463(1.10)/535(1.58)
435
–
330
0.94
–
0.01
338
1.23
Ag+
Mg+2
La+3
Li+
Mg+2
La+3
Li+
Ag+
Mg+2
La+3
Li+
Ag+
Mg+2
La+3
Li+
337
1.45
450(0.06)/542(0.05)
465(0.88)/545(0/98)
495(1.17)/525(1.18)
439
0.01/0.01
–
366
1.25
Photoindced changes in the band shape
370
1.09
307
1.15
0.04
–
VI
317/343
273/325
308
0.93/0.49
0.57/0.74
0.83
444(1/04)/540(1/40)
460(1/26)/498(1/50)/530(1/60)
436
–
0.04
<0.01
VII
308
0.79
436(0.05)
308
0.83
448(0.75)/536(0.95)
495(1.08)/526(1.18)
487
0.02/0.03
Photoindced changes in the band shape
328
0.55
260/320
260/320
260/328
263/340
323
0.94/0.73
0.92/0.73
0.66/0.67
0.78/0.55
0.90
0.08
<0.01
–
VIII
IX
500(0.14)
445(0.83)/545(1.40)
464(0.95)/538(1.57)
440
–
0.01
Ag+
Mg+2
La+3
320
0.97
490
<0.01
0.05
325
0.92
460
325
0.90
475(0.25)/493(0.28)/526(0.20)
0.16/0.14
a
ΔDBorig. is the optical density at the maximum of the absorption band of the colored product, which arises directly after the addition of the
metal salt to the acetonitrile solution prior to irradiation.
with metal ions (Table 3). Some changes were also
observed in the absorption bands in the UV region.
The irradiation of colored solutions with UV or visible
filtered radiation has no significant effect on the
absorption spectra, except for the colored products of
interaction of compounds V and VII with lanthanum
ions.
We believe that the latter fact shows the formation
of stable products of chemical interaction between the
molecules of photochromic derivatives of spiro
compounds with metal ions. The closeness of the
spectral characteristics of these products for all inves-
tigated hydrazones apparently indicates the similarity
of their nature and structure, practically independent of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

1436
POPOV et al.
the nature of the substituents at the phenyl ring of the
hydrazone fragment (Table 3).
reference HMDS. Spectrophotometric measurements
(photostationary spectra) of compounds in solution, the
kinetic curves of the processes of photocoloration and
spontaneous decoloration of the photoinduced forms
were carried out using a Cary 50 bio spectro-
photometer. As the solvent acetonitrile from Aldrich
was used, working concentration was 2×10–4 M. Mea-
surements were carried out in a quartz cell of 0.2 cm
thickness. For the study of the processes of complex
formation were used solutions of metal salts LiClO4,
AgClO4, Mg(ClO4)2, and La(NO3)3 in acetonitrile at a
ratio of the concentrations of the photochromic
compounds and metal ions 1:100.
In the case of univalent ions Li+ and Ag+
photoinduced changes of absorption spectra are
observed where after UV irradiation a new absorption
band appears in the visible spectrum. Similar photo-
induced spectral changes are observed in the case of
the photochromic hydrazones in solution containing
Li+ ions (Table 3).
Comparing the spectral data for the hydrazones in
the absence (Table 3) and in the presence of Li+ or Ag+
ions one can see that for most compounds a blue shift
of the absorption band of photoinduced form in the
case of the Li+ ions and a red shift with the Ag+ ions is
observed. It should be noted that spontaneous
relaxation of the photoinduced bands does not lead to
the full return of the molecules to the initial form A. In
some cases (compounds with strong electron-donor
substituents V and electron-acceptor substituents VII
and VIII) colored products are formed even before the
UV irradiation, including those displaying the
absorption bands observed for the products of interac-
tion with the ions Mg+2 and La+3 (compound V).
Irradiation of solutions was performed with filtered
light of a lamp Hamamatsu LC-4.
The objects of study were hydrazones based on
spiropyrans II–IX, obtained in the reaction of 7-hyd-
roxy-3',3'-dimethyl-3'H-spiro[chromen-2,1'-isobenzo-
furan]-8-aldehyde (I) with the acids hydrazides and N-
benzylthiosemicarbazide along the procedure [8].
Hydrazones (II–IX): To a solution of 0.001 mol of
aldehyde I [9] in 5 ml of ethanol was added a solution
of the corresponding hydrazide in a minimum amount
of ethanol. The mixture was refluxed for 15–30 min.
After cooling to room temperature the formed pre-
cipitate was filtered off, washed with minimum
amount of ethanol, and twice recrystallized from
acetonitrile.
Hydrazone (II). 1H NMR spectrum (DMSO-d6), δ,
ppm: 1.50 s, 1.67 s (6H, 3',3'-Me), 7.30–7.55 m (4H,
4',5',6',7'-Ar), 5.61 d (1H, 3-Ar, J3,4 9.50 Hz), 6.79 d
(1H, 4-Ar), 7.17 d (1H, 5-Ar, J5,6 8.30 Hz), 6.54 d (1,6-
Ar, 12.23 (1H, 6-Ar), 12.23 br.s, 12.05 br.s 7.88 (2H,
2,6-Ar, J2,3 = J6,5 = 7.54, 12.05 br.s (1Н, NH, OH),
8.76 s (1Н, CH=), 7.88 d (2Н, H2,6, Ph, J2,3 = J6,5 7.54),
7.30–7.55 m (2Н, H3,5, Ph), 7.30–7.55 m (1Н, H4, Ph).
The results of the study of the interaction between
molecules of synthesized spiropyran hydrazones and
metal ions suggest the formation of complexes of
different types. Under the influence of light, when the
spiropyran hydrazone molecules interact with
univalent ions Li+ or Ag+, apparently complexes are
formed between the ions and the phenoxide oxygen of
the merocyanine form (complexes of 1:1 composition,
LM). These complexes are characterized by the
induvidual absorption bands at 430–500 nm. The
appearance of structurized absorption band in the
visible spectrum at the interaction of spiropyran
hydrazone molecules with bivalent and trivalent metal
ions in the absence of light may be due to the
formation of complexes of the LM and L2M type [4].
1
Hydrazone (III). H NMR spectrum (DMSO-d6),
δ, ppm: 1.48 s, 1.64 s (6H, 3',3'-Me), 7.30–7.55 m (4H,
4',5',6',7'-Ar), 5.75 d (1H, 3-Ar, J3,4 9.60 Hz), 6.89 d
(1H, 4-Ar), 7.30 d (1H, 5-Ar, J5,6 8.40 Hz), 6.60 d(1H,
6-Ar12.37 br.s, (1Н, H6, Ph), 12.37 br.s, 12.18 br.s
(1Н, NH, OH), 8.77 s (1Н, CH=), 7.78 d (2Н, H2,6, Ph,
J2,3 = J6,5 8.10), 7.30 d (2Н, H3,5, Ph), 2.35 s (3Н, Ме).
Based on these data, it is difficult to formulate
definit conclusions on the structure of the obtained com-
plex compounds in solutions. The results of additional
studies on this subject will be published later.
EXPERIMENTAL
1
Hydrazone (IV). H NMR spectrum (DMSO-d6),
The IR spectra were recorded on a Varian Scimitar
δ, ppm: 1.51 s, 1.67 s (6H, 3',3'-Me), 7.30–7.50 m (4H,
4',5',6',7'-Ar), 5.61 d (1H, 3-Ar, J3,4 9.60 Hz), 6.79 d
(1H, 4-Ar), 7.16 d (1H, 5-Ar, J5,6 8.45 Hz), 6.53 d (1Н,
H6, Ph), 12.29 br.s, 11.91 br.s (1Н, NH, OH), 8.73 s
1
instrument in the range of 400–4000 cm–1, H NMR
spectra of solutions in DMSO-d6 were obtained on a
Varian Unity 300 spectrometer (300 MHz), internal
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SYNTHESIS, PHOTOCHROMIC PROPERTIES, AND COMPLEX FORMATION
1437
(1Н, CH=), 7.85 d (2Н, H2,6, Ph, J2,3 = J6,5 8.65), 6.93 d
(2Н, H3,5, Ph), 3.83 s (3Н, OМе).
(1H, 4-Ar), 7.13 d (1H, 5-Ar, J5,6 8.40 Hz), 6.49 d (1Н,
H6, Ph), 11.51 br.s, 9.98 br.s, 8.70 br.s (1Н, NH, OH),
8.33 s (1Н, CH=), 4.77 d (2Н, СН2, JНH 6.00), 7.20–
7.50 m (5H, Ph).
1
Hydrazone (V). H NMR (DMSO-d6), δ, ppm:
1.48 s, 1.65 s (6H, 3',3'-Me), 7.38–7.55 m (4H,
4',5',6',7'-Ar), 5.74 d (1H, 3-Ar,, J3,4 9.60 Hz), 6.88 d
(1H, 4-Ar), 7.26 d (1H, 5-Ar,, J5,6 8.40 Hz), 6.58 d (1,
6-Ar 12.51 (1Н, H6, Ph), 12.51 br.s, 11.96 br.s (1Н,
ACKNOWLEDGMENTS
This work was supported by the Federal Target
Program “Research and scientific-pedagogical staff of
nnovative Russia,” NK-190P-3, the State Contract P1266.
NH, OH), 8.73 s (1Н, CH=), 7.75 d (2Н, H2,6, Ph, J2,3
=
J6,5 9.00), 6.71 d (2Н, H3,5, Ph), 2.97 s (6Н, NМе2).
1
REFERENCES
Hydrazone (VI). H NMR spectrum (DMSO-d6),
δ, ppm: 1.48 s, 1.64 s (6H, 3',3'-Me), 7.30–7.50 m (4H,
4',5',6',7'-Ar), 5.74 d (1H, 3-Ar,, J3,4 9.60 Hz), 6.88 d
(1H, 4-Ar), 7.30 d (1H, 5-Ar, J5,6 8.40 Hz), 6.59 d (1H,
6-Ar (1Н, H6, Ph), 12.28 br.s, 12.23 br.s (1Н, NH,
OH), 8.75 s (1Н, CH=), 7.90–7.95 m (2Н, H2,6, Ph),
7.28–7.40 m (2Н, H3,5, Ph).
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1
Hydrazone (VII). H NMR spectrum (DMSO-d6),
δ, ppm: 1.48 s, 1.64 s (6H, 3',3'-Me), 7.30–7.50 m (4H,
4',5',6',7'-Ar), 5.76 d (1H, 3-Ar, J
9.60 Hz), 6.90 d
3,4
(1H, 4-Ar), 7.30 d (1H, 5-Ar, J5,6 8.40 Hz), 6.60 d (1Н,
H6, Ph), 12.28 br.s, 12.23 br.s (1Н, NH, OH), 8.75 s
(1Н, CH=), 7.90–7.95 m (2Н, H2,6, Ph), 7.28–7.40 m
(2Н, H3,5, Ph).
Hydrazone (VIII). 1H NMR spectrum (DMSO-d6),
δ, ppm: 1.51 s, 1.67 s (6H, 3',3'-Me), 7.30–7.50 m (4H,
4',5',6',7'-Ar), 5.63 d (1H, 3-Ar, J3,4 9.60 Hz), 6.80 d
(1H, 4-Ar), 7.20 d (1H, 5-Ar, J5,6 8.40 Hz), 6.55 d (1H,
6-Ar (1Н, H6, Ph), 12.33 br.s, 12.08 br.s (1Н, NH,
OH), 8.78 s (1Н, CH=), 8.13 d (2Н, H2,6, Ph, J2,3 = J6,5
8.80), 8.29 d (2Н, H3,5, Ph).
1
Hydrazone (IX). H NMR spectrum (DMSO-d6),
δ, ppm: 1.49 s, 1.66 s (6H, 3',3'-Me), 7.20-7.50 m (4H,
4',5',6',7'-Ar), 5.59 d (1H, 3-Ar, J3,4 9.60 Hz), 6.76 d
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012