Dyes and Pigments 83 (2009) 291–296

Contents lists available at ScienceDirect

Dyes and Pigments

j o u r n a l h o m e p a g e : w w w . e l s ev i e r . c o m / l o c a t e / d y e p i g

The synthesis and properties of novel, functional azobenzene based

metal complexes
a, b c
Xulin Xia *, Leong Huat Gan , Xiao Hu
a
School of Chemical Engineering, Anhui University of Technology, 59 Hudong Road, Maanshan, Anhui 243002, PR China
c
b Natural Science Academic Group, National Institute of Education, Nanyang Technological University, 1 Nanyang Walk, Singapore 637616, Singapore School of
Material Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore

article info abstract

Article history: Azobenzene-containing metal complexes with different carbon chain lengths connecting the azobenzene moiety and the
Received 14 February 2009
diamine ZnCl2 unit were characterized using spectrophotometric methods as well as thermal and X-ray diffractometric
Received in revised form 7
May 2009 analysis. The length of the chain between the azobenzene moiety and the diamine metal complex influences both the thermal
Accepted 7 May 2009 Available and fluorescent behaviour of the bi-functional compounds. Combining the azobenzene chromophore with the metal complex
online 13 June 2009 results in remarkably high azobenzene isomerization as well as two-band fluorescence emission centered at 290 and 560 nm
respectively, imparted by the metal complex component. A holographic image inscription and readout experiment of one of the
metal complexes in a poly(methyl methacrylate) matrix is described.
Keywords:
Metal complex
Azobenzene 2009 Elsevier Ltd. All rights reserved.
Photoisomerization
Photoresponsive
Photo-luminescence
Single crystal

1. Introduction Previously, azobenzene-based functional polymeric materials have been

described [9,10] which show promising photoresponsive characteristics. This
Azobenzene containing compounds have been intensively studied for both paper concerns further exploration of azo-benzene functionality by
theoretical and practical purposes for many years. They are widely connecting an azobenzene group to a Zn metal complex with the intention of
commercially available and are used as dyes and, more recently, have been combining the properties of the metal-complex with the extraordinary
applied to photoresponsive molecular switches and materials. They have physical characteristics of an azobenzene chromophore which might lead to
found broad application in nonlinear optics, optical storage media, the generation of novel materials.
chemosensors and optical switches [1–4]. For the purpose of realizing a
desired photo-responsive functionality, the development of new designs,
strate-gies, and the improvement of candidate materials have been undertaken 2. Experimental
enthusiastically in recent years.
2.1. General methods
Azo transitional metal complexes represent an interesting field of
azobenzene chemistry [5,6], as they combine the optical, redox, and magnetic Absolute ethanol, methanol, n-hexane, diethylether, acetone and
properties of the metal complex with the photo-isomerization properties of the chloroform were purchased from Aldrich and were stored over 4 Å molecular
azo functional group. The azo-benzene group as a ligand can form metal sieves. N,N-dimethyl formamide (DMF, Merck), tetrahydrofuran (THF,
complexes with transitional metals, such as Pt and Pd [7,8], as a consequence Fisher Scientific) were distilled under reduced nitrogen pressure from CaH 2
of bonding between the azo group and the transition metal, azo-benzene and subsequently stored over 4 Å molecular sieves. 4-Hydroxyazobenzene,
photoisomerization no longer occurs, a feature that limits the variety of 1,4-dibromobutane and 1,6-dibromohexane were purchased from Fluka and
azobenzene functionality. used as received.

1
H NMR spectra were recorded on a BRUKER 400 NMR spec-trometer
at 400 MHz in deuterated solvents with tetramethylsilane (TMS) as an
* Corresponding author. Fax: þ86 555 2311552. internal standard. IR spectra were recorded on a Perkin–Elmer FT-IR
E-mail address: xlxia@ahut.edu.cn (X. Xia). spectrometer 1725X on KBr discs. UV spectra

0143-7208/$ – see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2009.05.015
292 X. Xia et al. / Dyes and Pigments 83 (2009) 291–296

d
ppm

ature(ca. 60 C) for about 13 h. The salts formed were filtered with a Buchner
were recorded in various solvent using a Hewlett Packard UV/VIS 8425A funnel, then washed with acetone. The solvent of the filtrate was evaporated
diode array spectrophotometer, fluorescent measurements were made on an off by a rotary evaporator. The crude product was washed with very small
SHIMADZU RF-5301 PC spectrofluorophotometer. amount of ethanol and chloroform, then recrystallized from methanol twice
Thermal phase transitions were measured with a TA instrument 2920 and dried in
Modulated DSC using a scan speed of 5 C/min. Elemental analyses were vacuum oven at 40 C. Yield: 3.264 g (48.5%). m.p.:
performed using a Leco CHNS – 932 elemental analyzer. Crystallographic 86 C. (DSC, 10 C/min)
data were collected on a single crystal by Siemens P4 X-ray diffractometer 1
FT-IR (KBr, cm ): 2955 (aliphatic C–H stretch); 1606, 1504 (aromatic
with Mo Ka radiation by q/2q scan. The UV light for irradiation is generated C]C ring stretch); 1413 (–N]N–); 1255 (C–O stretch);
by a 500 W mercury lamp cooled by a circulated cooling water system with a 1
1144 (C–N); 835 (aromatic C–H, 1,4-disubstituted benzene ring). H NMR
2
light filter centered at 360 nm and the light intensity is ca 2.0 mw/cm . Azo- (CDCl3, 400 MHz): dppm ¼ 1.81 (m, 2H, –CH2CH2CH2
benzene photoisomerization experiments were carried out using a 1 cm quartz CH2Br), 1.96 (m, 2H, –CH2CH2CH2CH2Br), 3.78 (s, 2H, –(CH2)3
cuvette to measure absorbance changes immediately after the sample solution
in cuvette had been subject to UV light or heat treatment.

N=N OH + Br(CH2)nBr

K2CO3 CH3COCH3 Reflux

2.2. Synthesis and characterization of azobenzene-containing metal
complexes
(Ia, Ib)
N=N O(CH2)nBr +
The synthesis route for the metallomesogens IIIa, b is shown in Fig. 1.
NHCH2CH2N(C

2.2.1. Synthesis of 4-(4-bromobutyloxy) azobenzene(Ia) H3)2 CH3

To a 250 ml three-neck round bottomed flask, 7.05 mL (12.9 g, NaOH (C2H5)3N CH COCH 3 Reflux
3
60 mmol) 1,4-dibromobutane, 2.76 g (20 mmol) K2CO3, 0.12 g (0.7 mmol)
KI and 30 ml acetone were added. To a 250 mL pressure equalising dropping (IIa, IIb) N= N O(CH2)nNCH2CH2N(CH3)2
funnel, 4.0 g (20 mmol) 4-hydroxyazobenzene (HAZ) in 40 mL acetone were
ZnCl2 CH3
added. The HAZ solution was added drop-wise to the flask. The reaction CH3CH2OH
mixture was magnetically stirred and heated by an oil bath to a constant reflux
temper- CH3
(IIIa, IIIb) N= N O(CH2)nNCH2CH2N(CH3)2
2+
CH2Br), 4.12 (s, 2H, –CH2(CH2)3Br), 7.03 (d, 2H, ArH), 7.52 (m, 3H, ArH),
Zn
- - 7.93 (m, 4H, ArH).
Cl Cl
(n = 4: a; n = 6: b) Anal. Calcd for C16H17N2OBr: C, 57.67%; H, 5.41%; N, 8.41%.
Found: C, 57.24; H, 5.48%; N, 8.15%.
Fig. 1. The synthesis route for azobenzene-containing metal complexes.
2.2.2. Synthesis of 4-(6-bromohexyloxy)azobenzene (Ib)
The synthesis of 4-(6-bromohexyloxy)azobenzene (Ib) was accomplished
using an identical method to that used for 4-(4-bromobutyloxy)azobenzene
(Ia). Yield: 53%. m.p.: 76.1 C. (DSC, 10 C/min)

1
FT-IR (KBr, cm ): 2941 (aliphatic C-H stretch); 1605, 1501 (aromatic
C]C ring stretch); 1472 (–N]N–); 1258 (C–O stretch); 1143 (C–N); 842
(aromatic C–H, 1,4-disubstituted benzene ring).
1
H NMR (CDCl3, 400 MHz): dppm ¼ 1.57 (m, 4H, –CH2CH2(CH2)2
CH2CH2Br), 1.85–1.96 (m, 4H, –CH2CH2(CH2)2CH2CH2Br), 3.46 (t, 2H, –
(CH2)5CH2Br), 4.07 (t, 2H, –OCH2(CH2)5Br), 7.03 (d, 2H, ArH), 7.52 (m,
3H, ArH), 7.93 (m, 4H, ArH).
Anal. Calcd for C18H21N2OBr: C, 59.84%; H, 5.86%; N, 7.75%.
Found: C, 59.41; H, 5.69%; N, 7.62%.

0
2.2.3. Synthesis of 4-(4-(N,N,N -trimethylethylenediamino)butyloxy)
azobenzene(IIa)
To a 100 ml one-neck round bottomed flask connected to a condenser, 1.0
0
g (3 mmol) Ia, N,N,N –trimethylethylenediamine 0.88 mL (6.9 mmol),
NaOH 0.12 g (3 mmol), 0.42 mL (3 mmol) triethylamine and 25 mL acetone
were added. The mixture was magnetically stirred and heated in a water bath
to a constant reflux temperature(ca. 60 C) for 5 h. The solvent was evaporated
by rotary evaporator to near dryness. Ethyl acetate (15 mL) and benzene (15
mL) were added to extract the product. The organic solution was washed with
distilled water (10 mL) 3 times. The organic layer was separated and dried
with MgSO4. The organic solution was separated from MgSO 4 by pasteur
pipette. The solvent was evaporated to a constant weight using a vacuum
oven. The pasty product of IIa was 0.460 g. Yield: 43.3%.

1
H NMR (CDCl3, 400 MHz): ¼
1.60–1.80 (m, 4H,

–OCH2CH2CH2CH2–), 2.25 (s, 9H, –CH2(CH3)NCH2CH2N(CH3)2), 2.46

(m, 6H, –CH2(CH3)NCH2CH2N(CH3)2), 4.07 (t, 2H, –OCH2(CH2)3N–),
7.00 (d, 2H, ArH), 7.49 (m, 3H, ArH), 7.90 (m, 4H, ArH).
Anal. Calcd for C21H30N4O: C, 71.15%; H, 8.53%; N, 15.80%. Found:
C, 70.71; H, 8.67%; N, 15.43%.

0
2.2.4. Synthesis of 4-(6-(N,N,N -trimethylethylenediamino)hexyloxy)
azobenzene (IIb)
The synthesis of IIb was accomplished using an identical method to that
used for IIa with 61% yield.
1
FT-IR (KBr, cm ): 2941 (aliphatic C–H stretch); 1602, 1499 (aromatic
C]C ring stretch); 1475 (–N]N–); 1251 (C–O stretch); 1141 (C-N); 846
(aromatic C-H, 1,4-disubstituted benzene ring).
1
H NMR (CDCl3, 400 MHz): dppm ¼ 1.52–1.75 (m, 8H, –OCH2
(CH2)4CH2–), 2.25 (s, 9H, –CH2(CH3)NCH2CH2N(CH3)2), 2.46 (m, 6H,
–CH2(CH3)NCH2CH2N(CH3)2), 4.07 (t, 2H, –OCH2(CH2)5N–), 7.02 (d, 2H,
ArH), 7.49 (m, 3H, ArH), 7.90 (m, 4H, ArH).
Anal. Calcd for C23H34N4O: C, 72.21%; H, 8.96%; N, 14.65%. Found:
C, 71.73; H, 8.61%; N, 14.38%.

0
2.2.5. Synthesis of 4-(4-(N,N,N –trimethylethylenediamino)
butyloxy) azobenzene – zinc chloride complex (IIIa)
To a 10 mL flask, 0.05 g IIa dissolved in ca. 1.0 mL acetone was added. In
another 10 mL flask, 0.02 g freshly dried ZnCl 2 dissolved in ca. 1.0 mL
acetone was added. While under magnetic stirring, the ZnCl 2 solution was
added drop-wise to the solution of IIa . The mixture was then kept at
40 C for half an hour in a water bath before the solvent was
evaporated off. The solid obtained was recrystallized from
methanol and then recrystallized from ethanol.
 X. Xia et al. / Dyes and Pigments 83 (2009) 291–296 293

It was then washed with cold ethanol, finally dried in a vacuum oven. Yield:
A
42%.
m.p.: 151.6 C. (DSC, 10 C/min) 1 st heating
1
FT-IR (KBr, cm ): 2948 (aliphatic C–H stretch); 1602, 1501 (aromatic
C]C ring stretch); 1471 (–N]N–); 1254 (C–O stretch); 1143 (C–N); 839
(aromatic C–H, 1,4-disubstituted benzene ring).

Endotherm
1 2nd heating
H NMR (CDCl3, 400 MHz): dppm ¼ 1.82–1.96 (m, 4H, –OCH2 Cooling
CH2CH2CH2–), 2.58–3.13 (m, 15H, –CH2(CH3)NCH2CH2N(CH3)2), 4.10 (t,
2H, –OCH2(CH2)3N–), 7.02 (d, 2H, ArH), 7.49 (m, 3H, ArH), 7.90 (m, 4H,
ArH).
Anal. Calcd for C21H30N4OZnCl2: C, 51.39%; H, 6.16%; N, 11.42%.
Found: C, 51.30; H, 6.27%; N, 11.30%.

0
2.2.6. Synthesis of 4-(6-(N,N,N -trimethylethylenediamino)
hexyloxy) azobenzene – zinc chloride complex (IIIb)
The synthesis of IIIb was accomplished using an identical method to that
-50 0 50 100 150 200
used for IIIa with 40% yield.
Temperature (ºC)
m.p.: 158.4 C. (DSC, 10 C/min)
1
FT-IR (KBr, cm ): 2941 (aliphatic C–H stretch); 1603, 1504 (aromatic
C]C ring stretch); 1471 (–N]N–); 1258 (C–O stretch); 1144 (C–N); 841 B
(aromatic C–H, 1,4-disubstituted benzene ring).
1
H NMR (CDCl3, 400 MHz): dppm ¼ 1.40–1.96 (m, 8H, –OCH2
1 st heating
(CH2)4CH2–), 2.52–3.10 (m, 15H, –CH2(CH3)NCH2CH2N(CH3)2), 4.07 (t,
2H, –OCH2(CH2)5N–), 7.02 (d, 2H, ArH), 7.49 (m, 3H, ArH), 7.90 (m, 4H,
ArH). Endother Cooling
m
Anal. Calcd for C23H34N4OZnCl2: C, 53.24%; H, 6.61%; N, 10.80%.
Found: C, 53.14; H, 6.70%; N, 10.65%. 2nd heating

3. Results and discussion

3.1. Synthesis

The reaction between 4-hydroxyazobenzene and either 1,4-dibromobutane

or 1,6-dibromohexane was carried out using potassium carbonate and a
-50 0 50 100 150 200
catalytic amount of potassium iodide. The molar ratio had to be at least 3:1 of
Temperature (ºC)
1,4-dibromobutane (or 1,6-dibromohexane) to 4-hydroxyazobenzene to
ensure that only one bromine atom was substituted. Fig. 2. The DSC traces of IIIa (A) and IIIb (B).

0 phase transition [11] at about 79 C, and finally to an isotropic state transition

The product (Ia or Ib) was reacted with N, N, N -trimethyle-
at 151.6 C.
thelenediamine in an alkaline media with triethylamine to trap the produced
hydrobromide. The reaction was completed within several hours, but the The marked thermal phase differences between these two seemly similar
purification of the pasty product was difficult and included repeated compounds indicate that the carbon chain length (4 and 6 in this instance)
extraction with organic solvents and washing with aqueous acid and water between the azobenzene moiety and the diamine zinc complex has a vital
before drying in a vacuum oven at 40 C for 48 h. effect on whether different conglomerate states could be formed or not when
heat treatment is conducted.
The metal complexes were readily obtained by treating the diamine
ligands (IIa or IIb) with ZnCl2 in acetone. The crystalline products were 3.3. X-ray crystal diffraction analysis
grown from ethanol for IIIa or ethanol and acetone mixed solvent
2þ 2þ The crystal of IIIa grown at room temperature was examined by X-ray
(ethanol:acetone 1:5) for IIIb. Other transition metals, such as Cu , Ni and
2þ diffraction. The crystal structure and matrix arrangement are shown in Fig. 3
Co were also used to prepare azo-benzene containing metal complexes in
and Fig. 4 respectively. The crystal data and refinement for IIIa is listed in
the same manner as that of Zinc ion. However, none of these lead to the
formation of a metal complex. This feature could be explained by assuming Table 1. From the crystal structure and matrix arrangement it was found that
that the ligand trimethyl ethylene diamine, has a specific spacial configura- IIIa molecules are arranged in a head-to-head and tail-to-tail way, so that the
tion when connected with the azobenzene moiety which enables it to form static electronic
complex with Zinc rather than other metal ions tested.

3.2. Thermal analysis

Examination of the DSC traces of compounds IIIa and IIIb (Fig. 2),
revealed that IIIb exhibited one phase transition at about 158 C from crystal
phase to an isotropic melted phase. On the other hand, IIIa showed three
phase transitions i.e. from crystal to a glassy state at temperature around 10 C, Fig. 3. Molecular structure of the complex IIIa by X-ray crystal measurement. An ORTEP
then to a cold solid state drawing showing the atomic labeling scheme (H atoms omitted for clarity).
294 X. Xia et al. / Dyes and Pigments 83 (2009) 291–296

1.2
1.0 origin

0.8 40 s
Absorbance 90 s
0.6 160 s
250 s
350 s
0.4 470 s
640 s
0.2

0.0

300 400 500 600

Wavelength (nm)

Fig. 5. UV absorbance changes of IIIa solution in toluene under 360 nm UV irradiation.

absorption peak at 347 nm of trans azobenzene increased about 20% by heat

treatment at 70 C for 2.0 h even after the solution sample already had been
put in the dark for several days at room temper-ature. This phenomenon
shows that heat treatment of sample in the dark can speed the isomerization to
Fig. 4. The packing view along the b-axis of the complex IIIa. the more stable trans isomer and near hundred percent trans form azobenzene
sample could be obtained as long as sufficient heat treatment provided.
force of the metal complex and the van der Waals force of the conjugated
azobenzene group could be beneficial to the formation of the crystals. It can be seen from Figs. 5 and 6 that absorbance peak at 347 nm
decreased and the peak at 440 nm increased as the solution samples were
irradiated with UV light for different times due to trans-cis isomerization of
3.4. Azobenzene isomerization reaction induced by azobenzene moiety. After saturated UV light irra-diation, the cis-trans
UV light and thermal treatment isomerization could be induced by thermal treatment in the dark. The sharp
isosbestic points at 405 and 303 nm indicated that the azobenzene
The azobenzene zinc chloride complexes were irradiated with UV light to isomerization was the only process and is a reversible photo reaction.
explore their trans-cis isomerization phenomena. Figs. 5 and 6 show the UV Preliminary tests showed that after more than ten cycles of UV light induced
5 6 1 1
absorbance changes of IIIa dilute solution (4.3 10 M, 3 ¼ 2.3 10 M m ) trans-cis and thermally induced cis-trans isomerization cycles, the peak values
in toluene under the influ-ence of UV irradiation and heat treatment and positions were still maintained without noticeable change.
respectively.
Before the azobenzene isomerization measurement, the sample solutions Another remarkable feature of these azobenzene containing metal
were kept in dark for several days at room temperature and at elevated complexes is their isomerization efficiency. The percentage of the cis isomer
temperature, about 70 C, for several hours, to ensure that all of the of the azobenzene molecules after saturated UV irradiation is a very important
azobenzene units were in trans form. This process could be monitored by factor for both theoretical and application aspects. Assuming an initial all
observing the absorption peak increasing at 347 nm of trans form p–p* trans status, the cis isomer fraction after irradiation was determined from
transition until the absorbance reached a maximum value. One test showed spectro-photometric absorbance by equation (1) [12].
that

Table 1
1.0
Crystal data and structure refinement for IIIa.
0.8
Empirical formula C21H32Cl2N4OZn
Crystal system Monoclinic
Formula weight 492.78 49 min
Wavelength 1
0.71073 10 nm
Absorbance

0.6 21 min
Space group P21/C
Unit cell dimension a ¼ 22.609 Å, a ¼ 90 12.5 min
b ¼ 7.970 Å, b ¼ 106.13 9 min
c ¼ 14.054 Å, g ¼ 90 0.4 6 min
3
Volume, Z 2432.5 Å , 4 3.5 min
3 3
Density (calculated) 1.346 10 kg/m
3 1
1.5 min
Absorption coefficient 1.248 10 m
0.2 after irr
F(000) 1032
Crystal size 3
0.50 0.40 0.05 m
q range for data collection 1.88–25.00 0.0
Limiting indices 26 h 26, 9 k 1, 1 l 16
Reflection collected 5600
Independent reflections 4294 (Rint ¼ 0.0386) 300 350 400 450 500 550 600
Absorption correction Semi-empirical from psi-scan
Refinement method 2 Wavelength (nm)
Full-matrix least squares on F
2 1.036
Goodness-of-fit on F
Final R indices [I > 2s (I)] R1 ¼ 0.0554, wR2 ¼ 0.1205 Fig. 6. UV absorbance changes of IIIa solution in toluene under 80 C thermal treat- ment

after saturated UV irradiation.

 X. Xia et al. / Dyes and Pigments 83 (2009) 291–296 295

Table 2
IIa a
Relative fluorescent intensity of azobenzene ligands and metal complexes.
IIb
b Compounds
600 IIIa Intensity /lmax(nm)
Fluorescent intensity

IIIb IIa IIb IIIa IIIb

400
Band 1 1.00 1.05 4.30 4.23
l 303.0 304.5 298.5 288.0
max

Band 2 1.06 1.03 4.51 4.53

l 600.5 599.5 559.5 559.5
max
200 a
Excitation wavelength: 200 nm.
b
Fluorescent intensity values are based on integrated fluorescent intensities at the same
concentration in acetonitrile, Band 1 is in the range of 260–360 nm; band 2 is in the range of
520–650 nm.
0
2þ
Chelation Enhanced Fluorescence (CHEF) from Zn ion increases relative
fluorescent intensity of compounds IIa and IIb more than four-fold. Similar
CHEF effects were also reported from secondary amine ligands [14].
250 300 350 550 600 650 Noticeable features of the metal complexes IIIa, b are that two bands of
Wavelength (nm) emission centered at 290 nm and 560 nm respectively were found with a
similar magnitude of fluorescent emission intensity as compared with that of
Fig. 7. Fluorescence emission spectra of IIa, IIb, IIIa and IIIb in acetonitrile solvent. ligands IIa, b. It is well known that the azobenzene moiety does not show any
fluorescence because azobenzene is characterized by a shallow minima for
* *
Y singlet and triplet levels of both pp and np electronic configuration, as a
1 A=Ao (1)
consequence, the non-irradiative processes, which include trans-cis inter-
&cis ¼
½

1 3cis=3trans conversion, are very fast and compete efficiently with radiative process [15].
2þ
Where Ao is the initial absorbance of trans isomer at lmax absor-bance, A is We tentatively propose that 290 nm band emission is due to Zn ion induced
CHEF effect similar to the reported results [16]. 560 nm band emission may
the absorbance after saturated UV irradiation at the same wavelength, 3cis and be due to the azobenzene moiety, since it is bound to a relative heavy metal
3 trans are the molar absorption coeffi-cients of the pure cis and trans isomers complex, its degree of distortion is reduced, which in turn reduces its non-
respectively, the ratio of 3cis to 3trans, according to literature, is 0.055 for radiative process and increases its radiative intensity around 560 nm.
small azobenzene molecules [12].
The calculated results of [Y] cis were between 99.2 and 99.4% of cis
isomer after saturation with 360 nm UV light irradiation for the two
azobenzene containing metal complexes in diluted toluene solution. The 3.6. Holographic image formation
measurements and results could be repeated for many times without
noticeable deviation. These values are remarkably higher than the published
A tentative experiment to demonstrate holographic data storage
values of other azobenzene containing small molecules and polymers [12,13].
inscription and readout based on compound IIIa in a polymeric matrix
It is no doubt that such high isomerizing efficiency is advantageous to photo-
(PMMA) was successful. The experimental setup involves the routine dual
switching related applications.
laser beam interfering holographic grating formation setup [17]. Fig. 8 shows
original and reconstructed holographic images of the word SINGAPORE and
its emblem. The image was inscribed in a 150 mm thick PMMA film with 5.0
3.5. Fluorescence behavior of ligands and metal complexes
w% of IIIa evenly distributed throughout the matrix. The successful formation
of holographic image by interfering laser beams is believed to be due to the
The fluorescence measurements were carried out on IIa, IIb, IIIa and IIIb
6 6 unique multiphase formation/transition ability of IIIa. However IIIb was also
samples in dilute acetonitrile solutions (7.0 10 M for IIa and IIb and 4.4 10 tested under identical condi-tions but did not show any holographic
M for IIIa and IIIb). Fluorescence spectra are shown in Fig. 7, relative
inscription.
intensities of ligands and metal complexes are listed in Table 2. From Fig. 7
and Table 2, it can be seen that

Fig. 8. Holographic image formation based on IIIa in PMMA matrices. Left is the original image to be constructed, right one is the reconstructed hologram of the recorded image.
296 X. Xia et al. / Dyes and Pigments 83 (2009) 291–296

4. Conclusions [5] Ye ZH, De Boni L, Neves UM, Mendonça CR, Bu XR. Synthesis and two-photon
absorption property of novel salen complexes incorporated with two pendant azo dyes.
Tetrahedron Letters 2009;13:1371–3.
In the summary, two novel azobenzene-containing metal complexes IIIa, b [6] Tang HS, Zhu N, Yan VWW. Tetranuclear macrocyclic gold(i) alkynyl phosphine
were successfully synthesized and characterized. It was revealed that these complex containing azobenzene functionalities: a dual-input molecular logic with
two compounds had quite noticeable different thermal and other properties photoswitching behavior controllable via silver(I) coordination/decoor-dination.
Organometallics 2007;26:22–5.
arising from different spacer chain length connecting azobenzene [7] Curie M, Babic D, Marinic Z, Pasa-Tolic L. Synthesis and characterisation of Pd(II)
chromophore and metal-complex. UV light and thermal treatment showed 1
complexes with a derivative of aminoazobenzene: dynamic H-NMR study of
remarkable near hundred percent trans-cis and cis-trans isomerizing efficiency cyclopalladation reactions in DMF. Journal of Organometallic Chem-istry 2003;687:85–
99.
and this cycle was repeated 10 times without noticeable fatigue. Fluo-rescent [8] Ghedini M, Pucci D, Crispini A, Barberio G. Oxidative addition to cyclo-metalated
measurements showed that a CHEF effect of more than 4 fold the azobenzene platinum(ii) complexes: a route to octahedral liquid crystalline materials.
fluorescence intensity increment of metal complexes was achieved. Two Organometallics 1999;18:2116–24.
[9] Hu X, Zheng PJ, Zhao XY, Li L, Tam KC, Gan LH. Preparation, characterization and
emission bands centered at 290 nm and 560 nm from metal complexes in novel photoregulated rheological properties of azobenzene functional-ized cellulose
solution were observed. A holographic image was successfully stored using derivatives and their a–CD complexes. Polymer 2004;18: 6219–25.
IIIa in a polymeric matrix. These results show that an azobenzene moiety
[10] Zhao XY, Hu X, Yue CY, Xia XL, Gan LH. Synthesis, characterization and dual
covalently linked to a metal complex by a hydrocarbon chain may afford
photochroic properties of azo-substituted polythiophene derivatives. Thin Solid Films
various useful characteristics which may inspire practical applications. 2002;417:95–100.
[11] Seshadri T, Haupt HJ. Thermotropic properties of monosubstituted ferrocene derivatives
bearing bidentate N-benzoyl- N’-arylthiourea ligandsdnovel building blocks for
heterometallic liquid crystal systems. Journal Of Materials Chemistry 1998;8(6):1345–50.

[12] Morishima Y, Tsuji M, Kamachi M. Photochromic isomerization of azo-

Acknowledgements benzene moieties compartmentalized in hydrophobic microdomains in a microphase
structure of amphiphilic polyelectrolytes. Macromolecules 1992;25:4406–10.
We thank Dr Teng San Ong from Data Storage Institute of Singapore for [13] Wang WY, Wang MZ. Effect of a-cyclodextrin on the photoisomerization of azobenzene
the measurement of holographic image inscription and readout experiment. functionalized hydroxypropyl methylcellulose in aqueous solu-tion. Polymer Bulletin
2007;59:537–44.
[14] Inoue MB, Munoz IC, Inoue M, Fernando Q. X-ray structures and fluorescence spectra of
2þ 2þ
binuclear Zn and Cd complexes of an amide-based naph-thalenophane. Inorganica
Chimica Acta 2000;300:206–11.
References [15] Ghedini M, Pucci D, Crispini A, Aiello I, Barigelleli F. Dinuclear cyclopalladated
azobenzene complexes: a comparative study on model compounds for organometallic
[1] Natansohn A, Rochon P. Photoinduced motions in azo-containing polymers. Chemical liquid-crystalline materials. Applied Organometallic Chemistry 1999;13:565–81.
Reviews 2002;102:4139–76.
[2] Muraoka T, Kinbara K, Kobayashi Y, Aida T. Light driven open-close motion of chiral [16] Bernardo MA, Pina F, Garcia-Espana E, Latorre J, Luis SV, Llinares JM. Ther-
molecular scissors. Journal of the American Chemical Society 2003;125: 5612–3. modynamic and steady-state fluorescence emission studies on metal complexes of
receptors containing benzene subunits. Inorganic Chemistry 1998;37:3935–42.
[3] Cheelham AG, Hutchings MG, Claridge TDW, Anderson HL. Enzymatic synthesis and
photoswitchable enzymatic cleavage of a peptide-linked rotaxane. Angewandte Chemie [17] Manickasundaram S, Kannan P, Hassan QMA, Palanisamy PK. Azo dye based
International Edition 2006;45:1596–9. poly(alkyloxymethacrylate)s and their spacer effect on optical data storage. Journal of
[4] Nashihara H. Combination of redox- and photochemistry of azo-conjugated metal Materials Science: Materials in Electronics 2008;19: 1045–53.
complexes. Coordination Chemistry Review 2005;249:1468–75.