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Synthesis, characterization and optical limiting properties of a gallium

phthalocyanine dimer
Helmut Bertagnolli,*a Werner J. Blau,b Yu Chen,c Danilo Dini,d Martin P. Feth,a Sean M. O’Flaherty,b
Michael Hanack*d and Venkata Krishnana
Received 13th August 2004, Accepted 20th October 2004
First published as an Advance Article on the web 24th November 2004
Published on 24 November 2004. Downloaded by FAC DE QUIMICA on 20/03/2014 19:49:21.

DOI: 10.1039/b412546k

A gallium phthalocyanine dimer with a direct gallium–gallium bond, [tBu4PcGa]2?2dioxane (2),

has been synthesized and characterized by Extended X-ray Absorption Fine Structure (EXAFS)
spectroscopy, UV/Vis, IR, NMR and MALDI-MS. By EXAFS the gallium–gallium distance
in 2 was found to be 2.46 Å. Dimer 2 exhibits reverse saturable absorption with significantly
reduced saturation intensity with respect to the starting material tBu4PcGaCl (1) as determined by
means of optical limiting experiments.

Introduction [tBu4PcIn]2?2tmed by a Wurtz coupling reaction of tBu4PcInCl

Optical limiting (OL) is an important application of nonlinear
optics, useful for the protection of human eyes, optical
elements and optical sensors from intense laser pulses.
Phthalocyanines (Pcs) are materials that optically limit
nanosecond light pulses in a fairly wide range of the UV/Vis
spectrum via excited state absorption processes. The nonlinear
optical absorption mechanism of phthalocyanines in the
optical region comprised between Q- and B-bands involves
the population of excited states which absorb more effectively
than the ground state. This gives rise to the phenomenon of
Reverse Saturable Absorption (RSA) as a consequence of
multiphoton absorption.1 It has been shown that phthalocy-
anine compounds exhibit RSA because of the occurrence of
intersystem crossing from the lowest excited singlet state (S1)
to the lowest triplet state (T1) and the subsequent increase
in the population of the strongly absorbing T1 state with
nanosecond dynamics.2–4
Axial substitution on phthalocyanines generally increases
their solubility and, therefore, reduces molecular aggrega-
tion.4c,4d In terms of OL effectiveness in the visible range,
axial substitution can improve the efficiency of excited state
absorption through the inhibition of the decay of the excited
state formed in a nonlinear optical regime.1a,4a,c–e,k Moreover,
axial substituents in Pcs influence favourably nonlinear
optical absorption for the presence of a dipole moment
perpendicular to the macrocycle in the axially substituted
phthalocyanines.4c,d,o The exploitation of the chemical reac-
tivity of the bond M–Cl [M 5 Ga3+, In3+] and MLO [M 5 Ti4+,
etc.] bonds can allow the preparation of a series of highly
soluble axially substituted and bridged Pc complexes.4f,k
Organometallic compounds containing metal–metal single
bonds between the metallic elements of Group 3A (Al, Ga, In,
Tl) are unusual but can be of interest in the field of material
sciences.5 Recently4f,j we have prepared the first dimeric
indium phthalocyanine complex with an indium–indium bond
*h.bertagnolli@ipc.uni-stuttgart.de (Helmut Bertagnolli)
hanack@uni-tuebingen.de (Michael Hanack)
in the presence of N,N,N9,N9-tetramethylethylenediamine
(tmed). The role of the neutral tmed ligand is mainly to
promote maximum coordinative saturation at the indium
center. By EXAFS measurements the In–In distance was
found to be 3.24 Å.4,5 The OL response is generally enhanced
by dimerization.4j,k
Similarly, the synthesis and molecular structure of organo-
gallium compounds with a Ga–Ga bond are also an interesting
area of study.6 A number of novel organogallium compounds
with a gallium–gallium bond, for example, Ga2R2(m-O2CCH3–
O,O9)2 [R 5 CH(SiMe3)2] 7, [Ga2Cl4(dioxane)2]x 8, [(Me3Si)2-
C(Ph)C(Me3Si)NGaCl]2 9 and [(Me3Si)2HC]4Ga2,10 have been
reported so far. Herein we report on the synthesis, structural
characterization and nonlinear optical properties (OL pro-
perties), of a gallium phthalocyanine dimer with a direct
bond between central atoms,11 i.e. [tBu4PcGa]2?2dioxane (2)
(Scheme 1). Dimer 2 is prepared in 83% yield by the reaction of
soluble tBu4PcGaCl (1)4a with activated magnesium in freshly
dried THF and in the presence of 1,4-dioxane. The resulting
dimer exhibits an enhancement of OL response at the
same wavelengths when compared to the parent monomer
tBu4PcGaCl (1).
Results and discussion
For most of the phthalocyanines and naphthalocyanines, it is
very difficult to obtain suitable single crystals required for
X-ray structural determination. In such cases, EXAFS
(extended X-ray absorption fine structure) spectroscopy is
considered to be a powerful technique for the determination of
the local structure of a specific atom, regardless of the state of
the sample. EXAFS provides information on the coordination
number, the nature of the scattering atoms surrounding the
absorbing (excited) atom, the interatomic distance between the
absorbing atom and the back-scattering atoms and the Debye–
Waller factor, which accounts for the disorders due to static
displacements and thermal vibrations.12 In this study, the
formation of the gallium–gallium bond in 2 was initially
confirmed by EXAFS spectroscopy. The experimentally

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Table 1 EXAFS determined structural data of [tBu4PcGa]2?2dioxane

(2)
Na r/Åb s/Åc

Ga–NPyrrole/ODioxane 5 2.00 ¡ 0.02 0.067 ¡ 0.007

Ga–C 8 3.00 ¡ 0.03 0.071 ¡ 0.016
Ga–NAza 4 3.33 ¡ 0.04 0.081 ¡ 0.026
Ga–Ga 1 2.46 ¡ 0.03 0.095 ¡ 0.016
a
N 5 coordination number. b r 5 interatomic distance between the
absorber and the back-scatterers. c s 5 Debye–Waller factor with
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calculated standard deviations.

Fig. 2 EXAFS structure of [tBu4PcGa]2?2dioxane (2).

Scheme 1
determined and fitted EXAFS functions of 2 are shown in k
space as well as by Fourier transforms in real space in Fig. 1.
The structural parameters along with the estimated errors
arising from the refinement analysis are summarized in Table 1.
The molecular structure of 2 is given in Fig. 2. In the fitting
procedure, the intramolecular coordination numbers were
fixed to the known values for the ligands around the gallium
atom in the complex. The other parameters including
intermolecular coordination number, interatomic distances,
Debye–Waller factor and energy zero value were determined
by iterations. The analysis of the data shows the contribution
of the phthalocyanine macrocycle in the spectra. Owing to the
similar back-scattering behavior of nitrogen and oxygen,
occurring at nearly the same distance from the metal atom, a
combined shell with a coordination number of five was
determined at a distance of about 2.00 Å. This includes the
four back-scattering nitrogen atoms from the pyrrole and the
one back-scattering oxygen atom from the dioxane ligand.
Another four back-scattering nitrogen atoms from the aza
nitrogen atoms were found at 3.33 Å distance. Further, an
additional shell consisting of eight carbon atoms, having
gallium–carbon distances at 3.00 Å was observed. The fit was
significantly improved by having a gallium–gallium distance
with a coordination number of one at a distance of 2.46 Å.
For comparison, the reported gallium–gallium bond
lengths in some organogallium compounds are 2.38 Å for
Ga2R2(m-O2CCH3–O,O9)2,7 2.38 Å for [Ga2Cl4(dioxane)2]x,8
2.45 Å for [(Me3Si)2C(Ph)C(Me3Si)NGaCl]2,9 and 2.56 Å for
[(Me3Si)2HC]4Ga2.10 When the coordination number for

Fig. 1 Experimental (solid line) and calculated (dotted line) EXAFS functions (a) (k range: 2.6–15.0 Å21, fit index: 32.66, DE0: 13.83 eV) and their
Fourier transforms (b) for [tBu4PcGa]2?2dioxane measured at the Ga K-edge at 10 367 eV.

684 | J. Mater. Chem., 2005, 15, 683–689 This journal is ß The Royal Society of Chemistry 2005
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gallium was iterated, it resulted in a value of 0.7, which was

close to unity, and therefore the coordination number was
fixed to one. This result is consistent with an arrangement of
the complex as a dimer. In addition, it should be noted that
the back-scattering behavior of Ga (Z 5 32), Cl (Z 5 17) and
I (Z 5 53) are different, thus these elements can be well
distinguished by EXAFS spectroscopy, especially when these
back-scatterers occur in a distance-range of 2–3 Å. We did not
find any evidence that this compound is tBu4PcGaI, a possible
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by-product.
The effect of the metal ions on the phthalocyanine ring in
the metallophthalocyanines has been widely studied.13 To the
best of our knowledge, the shortest interplanar ring spacing in
gallium phthalocyanines was found to be 3.34 Å in the case of
Ga(Pc)Cl for a parallel stacking arrangement.14a When such a
short interplanar ring spacing is assumed in the present case,
the intermolecular metal–metal distance should be about
3.35 Å, but the EXAFS results indicate the gallium–gallium
distance to be 2.46 Å, which supposes that the two gallium
atoms in the molecule are projected inwards of the phthalo-
cyanine ring and that the gallium center is located 0.45 Å out
of the plane formed by the four coordinated nitrogen atoms. In
addition, when a rigid phthalocyanine molecule with an
average cavity diameter of about 3.85 Å, which is not
deformed by the metal atom is assumed, the shortest metal–
nitrogen distance occurs at 1.97 Å.15,16 But the present results
indicate a gallium–nitrogen and a gallium–oxygen distance of
2.00 Å, which also supposes that the gallium center is located
0.45 Å out of the plane. This value is in good agreement with
the reported out-of-plane value of 0.439 Å in crystalline
PcGaCl.14a Further, in a rigid phthalocyanine molecule, the
shortest distance between the metal center and the nearest
carbon occurs at 2.96 Å, while in the present case it results a
gallium–carbon distance of 3.00 Å. From these values an out-
of-plane location of gallium equal to 0.54 Å was found, which
is in agreement with the value determined from the shortest
gallium–nitrogen separation values. Since the complex was
found to be a dimer, it is believed that the t-butyl groups in the
periphery of the macrocycles have no steric hindrance with
each other and the two phthalocyanine macrocycles are
arranged in a staggered conformation. In any case, the exact
geometry of these groups cannot be determined by EXAFS
spectroscopy since a mixture of regioisomers is present.
Further, the sterically less crowded staggered conformation
is preferred when interplanar spacing is less than 3.5 Å,
whereas the eclipsed conformation occurs at larger spacings.14b
The linear absorption spectra of tBu4PcGaCl (1) and dimer
2 are presented in Fig. 3(a). The similarity of the UV/vis
spectra of 1 and 2 shows that dimerization does not affect
considerably the spectral profile. In fact, the positions of
the maxima of optical absorption are practically unaltered
(693 and 695 nm for the Q-band absorption of 1 and 2,
respectively). This implies that the two Pc rings in the Ga–Ga
bridged dimer do not modify considerably the electronic
distribution of each other. The extent of electronic conjugation
in both compounds 1 and 2 is practically the same since
compound 2 has a gallium–gallium single bond of s-type with
no presence of delocalized electrons. As expected, the main
differences between the spectral features of 1 and 2 are related
Fig. 3 UV/Vis spectra (a) and photoluminescence spectra (b,
lex 5 355 nm) of tBu4PcGaCl (1) and [tBu4PcGa]2?2dioxane (2) in
chloroform.
to the change of the molar extinction coefficient due to the
different number of absorbing Pc rings per molecular unit4o in
passing from the monomer to the Ga–Ga bridged dimer.
Photoluminescence spectra in dilute chloroform solutions
have also been obtained under the same conditions of the
spectra of Fig. 3(a) when the wavelength of excitation was
355 nm [Fig. 3(b)]. In Pcs, such a wavelength of excitation
corresponds to the energy necessary for the occurrence of
the transition HOMO (21)A LUMO, which originates the
B-band absorption [Fig. 3(a)].17 Upon emission, both com-
pounds 1 and 2 display a Stokes shift of the emission peak with
respect to the location of the Q-band absorption [Fig. 3(b)].
Different to the absorption spectra, dimerization influences
the energy of emission more strongly, since the extent of the
Stokes shift is larger for the monomer with respect to the
dimer. Maximum emission peaks for 1 and 2 are found at 713
and 700 nm, respectively. Such a difference could be ascribed
to the more rigid structure of the dimer with respect to the
monomer. This means that the dimer relaxes radiatively from
the electronic excited state p* in a higher vibrational level.18
As shown in Fig. 4, the main differences in the IR spectra
between 1 and 2 are: (a) the absence of the absorption band of
the Ga–Cl stretching mode at 351 cm21 in the IR spectrum of
the dimer; (b) a striking increase in the relative intensity, and
broadening, of some characteristic absorption peaks in 2 with
respect to tBu4PcGaCl (1); and (c) some new absorption peaks,
e.g. at 802 and 393 cm21 and others, are observed.
The molecular peak of [tBu4PcGa]2?2(1,4-dioxane) (2) was
found in the Matrix Assisted Laser Desorption (MALDI) mass
spectrum. This appeared at m/z 5 1789 (calc. m/z 5 1788.8).

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Fig. 4 IR spectra of (top) tBu4PcGaCl (1) and (bottom)
[tBu4PcGa]2?2dioxane (2).
There was no evidence that this peak resulted from an in-situ
by-product formed under the MALDI-MS experimental
conditions. For the starting material tBu4PcGaCl (1), we did
not observe the formation of tBu4PcGa–GaPctBu4 under the
same experimental conditions.
tBu4PcGaCl (1) is a mixture of four structural isomers.4a,19
We have been the first to separate the isomers of tetrasub-
stituted Pcs and undertake detailed and extensive NMR
studies probing the influence of isomers on the NMR spectra
of the Pcs.20 The NMR spectrum of an isomeric mixture is
somewhat different from the pure isomers, but it is still
possible to draw definite conclusions about the structure. The
main reason that we took a tetrasubstituted and not an
octasubstituted Pc as a mode compound is the higher solubility
of the tetrasubstituted over the octasubstituted Pc.19 As
expected, the 1H NMR spectrum of 2 measured in CDCl3 is
somewhat more complicated than that of 1 because of the ring-
current effect caused by the two macrocycles and the possible
existence of rotational isomers. In 2, the aromatic proton
signals are broadened, and appear at d 8.8–9.3 ppm (multi-
plet), and 8.2–8.3 ppm (multiplet), respectively, and the tBu
protons at 1.9 ppm. The proton signals for free 1,4-dioxane
appear at d 3.3 ppm (s, 8H), whereas the corresponding proton
signals for the coordinated 1,4-dioxane ligands in 2 are found
at d 3.7 and 4.2 ppm, respectively, due to the asymmetry of the
1,4-dioxane coordinated with the gallium atoms. The observed
downfield shift would normally not be expected; here it may be
explained, that the coordinating molecules do not fit into the
cone of the ring-current.4f In the 13C NMR spectrum
the aromatic carbon signals of 2 are very similar to those of
the starting compound 1, and can easily be assigned to the
appropriate carbon atoms in the macrocycle. In comparison
with free 1,4-dioxane, whose 13C NMR signals appear at
66.6 ppm (for four equivalent carbon atoms), the carbon
signals of the coordinated 1,4-dioxane moved downfield
slightly and are located at d 67.9 and 68.2 ppm, respectively.
In phthalocyanine materials, optical nonlinearities are of
interest as they can be large with short (less then 1 ps) response
686 | J. Mater. Chem., 2005, 15, 683–689
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times. For the NLO characterization of Pcs the Z-scan
technique has been used.21 Herein, the Z-scan in the open-
aperture mode21 was employed to investigate the nonlinear
optical absorptive properties of the phthalocyanine com-
pounds tBu4PcGaCl (1) and [tBu4PcGa]2?2dioxane (2). In this
technique the transmittance of a focused Gaussian laser beam
is monitored as a function of the position of the sample passing
through the focus of the collimated beam. The nonlinear
absorption coefficient (bI) was calculated as a function of
incident focal intensity (I0).
All open-aperture Z-scans performed in this study, from
both compounds, exhibited a reduction in the transmission
about the focus of the lens. This was typical of an induced
positive nonlinear absorption of the incident light, in this case
attributed to excited state absorption. It was noticed that the
effective nonlinear absorption coefficient bI, in all cases, was
not stationary with respect to the intensity at the focus. The
nonlinear absorption coefficient bI plotted as a function of the
incident focal intensity I0 is depicted in Fig. 5 for 1 and 2,
where each data point on the plot represents an independent
open-aperture Z-scan of the compound in question and the
solid lines are sketched merely as guides to the eye. It can
clearly be seen that bI reduces in magnitude with increasing
focal intensity I0 in the figure. Despite this, effective third
order nonlinear absorption coefficients bI can be estimated by
suitably interpolating the data in Fig. 5 at certain on-focus
intensities. For example, bI values interpolated for an irradia-
tion value of 0.5 GW cm22 (arbitrarily chosen) are quoted as a
sample case study in Table 2. It can be seen that both
compounds exhibit similar nonlinear absorption coefficients
with 2 tending to exhibit a larger bI than 1 at lower I0 values.
The normalized transmission (TNorm) against the incident
fluence F per pulse [F 5 E/pw(z)2, where E is the incident
energy per pulse and w(z) is the beam waist as a function of z in
the experiment] was analyzed to further investigate the non-
linear absorption. The nonlinear absorption coefficient a(F,
FSat, k),4j where a(F, FSat, k) # a0(1 + F/FSat)21(1 + kF/FSat)
was used to fit the normalized transmission as a function of
this energy density to a superposition of all open-aperture
Fig. 5 Plot of effective nonlinear absorption coefficient bI against the
on-focus beam intensity I0 for both compounds. Each data point
represents an independent open-aperture Z-scan and the solid lines are
intended as a guide to the eye.
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Table 2 Summary of the nonlinear optical properties for tBu4PcGaCl (1) and [tBu4PcGa]2?2dioxane (2) in toluene
Compound c/g L21 a0/cm21 I0/GW cm22
1 0.5 1.1 0.5
2 0.5 1.3 0.5
datasets for each compound. This expression assumes an ideal
three level absorption system where F represents the fluence,
FSat the saturation fluence and k the ratio of the excited to
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ground state absorption cross sections sex/s0. The parameters
k (realistically sex and a0 were measured) and FSat were treated
as free constants in the fitting. The plots of TNorm against
energy density are depicted in Fig. 6 and the a0, k and FSat
values for each compound are also presented in Table 2. It was
found that compound 2 exhibits a significantly lower FSat than
that of 1, by approximately a factor of 3. The ratio of their
excited and ground state absorption cross sections is similar
with 1 exhibiting a k coefficient approximately 1.35 times that
of 2. Thus, dimerization of 1 in the manner described here to
yield in 2 is clearly a viable method of tuning the saturation
energy density (FSat) of the material, reducing it by a factor of
3. This reduction in FSat is coupled with a slight increase of bI
at low incident intensity and with approximately equivalent
bIs at higher intensities. The k coefficient is reduced by
approximately 22% after dimerization of 1 to 2 but this can
probably be mostly attributed to the increase in linear
absorption coefficient by approximately 18% over the same
molecular modification.
Recently we have reported on the optical limiting of a Pc
dimer with a direct In–In bond.4j In this study we compared
the starting tBu4PcInCl with the new [tBu4PcIn]2?2tmed
compound. Similar to the results presented in this study for
the Ga–Ga Pc dimer 2 we found that dimerization of the
starting single In unit reduced FSat by a factor of approxi-
mately 2.5 (comparable to a factor of approximately 3 for the
Ga–Ga dimer presented here). The In–In Pc dimer also
exhibited a slightly lower FSat of (24.2 ¡ 0.8) J cm22 than that
of compound 2 presented here. The reduction of k for the In
Pcs by a factor of about 2.2 after dimerization is far more
Fig. 6 Plots of normalized transmission against incident pulse energy
density for (a) tBu4PcGaCl (1), and (b) [tBu4PcGa]2?2dioxane (2). The
solid lines are theoretical curve fits.
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bI/cm W21 FSat/J cm22 k (sex/s0)
(3.2 ¡ 0.6) 6 1028 27.0 ¡ 1.0 13.5 ¡ 0.4
(3.5 ¡ 0.7) 6 1028 8.9 ¡ 0.4 10.4 ¡ 0.3
significant that the reduction by a factor of 1.3 for the Ga
compounds presented here. This difference, however, can be
partially attributed to the particularly low linear absorption
coefficient of the tBu4PcInCl molecule, which allows it to
exhibit a large k coefficient compared to other Pcs.4l
Conclusions
A gallium phthalocyanine dimer 2 with a direct gallium–
gallium bond was prepared by the reaction of soluble
tBu4PcGaCl with activated magnesium turnings in freshly
dried THF in the presence of 1,4-dioxane in 83% yield. From
the EXAFS measurements the intermolecular gallium–gallium
distance was determined at 2.46 Å and the gallium metal center
is supposed to be located 0.45 Å out-of-plane from the
phthalocyanine ring. Dimer 2 exhibits a significantly reduced
saturation intensity, determined via optical limiting experi-
ments, relative to the starting material tBu4PcGaCl (1). This
reduction in the saturation energy density is coupled with a
slight increase of nonlinear absorption coefficient (bI) at low
incident intensity and with approximately equivalent bIs at
higher intensities. Further investigations of the nonlinear
optical properties and other interesting photophysical proper-
ties of thin films of compounds 1 and 2 are currently in
progress.
Experimental
General
The operations for synthesis prior to the termination reaction
were carried out under purified dry nitrogen. Solvents were
purified, dried and distilled under dry nitrogen. FT-IR: Perkin-
Elmer Spectrum 1000; UV/Vis: Shimadzu UV-365; MALDI-
MS: Bruker Biflex (preparation method of sample: the samples
were dissolved in CH3CN, then mixed 1 : 1 (0.8 ml each) with a
methanol solution of a-cyano-4-hydroxycinnamic acid as
matrix); 1H-, 13C-NMR: Bruker AC 250 (1H: 250.131 MHz,
13
C: 62.902 MHz).
The EXAFS measurements of the complex were performed
at the Ga K-edge at 10 367 eV at the beamline X1.1 of the
Hamburger Synchrotron Radiation Laboratory (HASYLAB)
at DESY, Hamburg. The complex was measured with a
Si(111) double crystal monochromator at ambient conditions.
The positron energy was 4.45 GeV and the beam current was
about 120 mA. Data were collected in transmission mode with
ion chambers filled with nitrogen gas. Energy calibration was
monitored using 20 mm thick iridium metal foil having the L3-
edge at 11 215 eV. The sample was prepared as a pellet of a
mixture of the complex with polyethylene. The data were
analyzed with a program package especially developed for
the requirements of amorphous samples.22 The program
AUTOBK23 was used for the removal of background and
J. Mater. Chem., 2005, 15, 683–689 | 687

the program EXCURV9224 was used for the evaluation of the
EXAFS function. Curved wave theory was used for the data
analysis in k space and the resulting EXAFS function was
weighted with k3. The mean free path of the scattered electrons
was calculated from the imaginary part of the potential (VPI
set to 24.00), the amplitude reduction factor AFAC was fixed
at 0.8 and an overall energy shift DE0 was introduced to give a
best fit to the data.
All Z-scan experiments described in this study were
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performed using 6 ns pulses from a Q switched Nd:YAG
laser. The beam was spatially filtered to remove the higher
order modes and tightly focused with a 9 cm focal length lens.
The laser was operated at its second harmonic, 532 nm, with a
pulse repetition rate of 10 Hz. The samples were prepared
at 0.5 g L21 in toluene followed by gentle agitation for ca.
20 minutes in a low-power (60 W) sonic bath to ensure
complete and uniform dispersal. All subsequent measurements
were performed in quartz cells with a 1 mm path length.
Synthesis of gallium phthalocyanine dimer 2
To a suspension of magnesium turnings (0.5 g, 20.57 mmol),
previously activated by means of an ultrasonic bath under
reduced pressure, in anhydrous 1,4-dioxane (20 ml, Aldrich
product) was added a solution of tBu4PcGaCl 4a (0.3 g,
0.36 mmol) in anhydrous 1,4-dioxane (30 ml) and a catalytic
amount of iodine (10 mg, 0.04 mmol) under argon. After
refluxing at 110 uC for 48 h, the reaction solution was
transferred into a pressure equalizing fritted glass funnel
containing a small quantity of glass wool to hold back excess
solid magnesium. The obtained filtrate was evaporated to
dryness under high vacuum. To further remove any inorganic
impurity, the crude product was dissolved in dry toluene,
stirred, filtered (this procedure was repeated several times),
dried at 60 uC in vacuo to afford a blackish-green solid
powder in 83% yield (0.264 g). MALDI-MS (m/z): calc. for
C104H112Ga2N16O4: 1788.8; found: 1789. UV/Vis (CHCl3):
lmax(nm) 5 693, 664(sh), 625, 356. PL (CHCl3, lexc 5 355 nm):
lmaxfluor (nm) 5 707; FTIR (KBr, cm21): 2962(ms), 2922(m),
2857(m), 1779(w), 1723(w), 1613(m), 1506(m), 1482(m),
1458(m), 1407(m), 1394(m), 1363(m), 1333(ms), 1260(vs),
1199(m), 1144(m), 1087(vs), 1051(s), 1022(vs), 967 (w),
929(ms), 9167(w), 893(w), 863(m), 803(vs), 764(m), 749(s),
737(m), 694(m), 670(m), 601(w), 566(w), 531(m), 518 (vw),
442(w), 390(m). 1H NMR (CDCl3): d/ppm 5 1.9(m, 72H, tBu),
8.2–8.3(m, 8H, H-1), 8.8–9.3(m, 16H, H-2, 20), 3.7 and 4.2(m,
H-dioxane). 13C NMR (CDCl3): d/ppm 5 32.1 (tBuCH3),
36.2(CMe3), 118.9–119.6(C-20), 122.6–123.0(C-2), 128.5(C-1),
133.5–134.1(C-3), 135.8–136.6(C-30), 150.8–151.7(C-4,40),
154.2–154.5(C-10).
Acknowledgements
This research was supported by Deutsche
Forschungsgemeinschaft (Ha 280/165-1) and EU project
HPRN-CT-2000-00020. Y. C. thanks the Alexander
von Humboldt Foundation of Germany for a fellowship.
The Dublin group acknowledges support by the Irish
Higher Education Authority and Enterprise Ireland, and
lab assistance from Ms S. V. Hold. We also thank
688 | J. Mater. Chem., 2005, 15, 683–689
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HASYLAB, Hamburg for the support for synchrotron
radiation experiments.
Helmut Bertagnolli,*a Werner J. Blau,b Yu Chen,c Danilo Dini,d
Martin P. Feth,a Sean M. O’Flaherty,b Michael Hanack*d and
Venkata Krishnana
a
Institut für Physicalische Chemie, Universität Stuttgart,
Pfaffenwaldring 55, 70569 Stuttgart, Germany.
E-mail: h.bertagnolli@ipc.uni-stuttgart.de; Fax: +49-(0)711-6854443;
Tel: +49-(0)711-6854450
b
Materials Ireland Polymer Research Centre, Department of Physics,
Trinity College Dublin, Dublin 2, Republic of Ireland
c
Department of Chemistry, East China University of Science and
Technology, 130 Meilong Road, Shanghai 200237, People’s Republic of
China
d
Institut für Organische Chemie, Universität Tuebingen, Auf der
Morgenstelle 18, D-72076 Tuebingen, Germany.
E-mail: hanack@uni-tuebingen.de; Fax: +49-(0)7071-295268;
Tel: +49-(0)7071-2972432
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