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Spectroscopic properties of monolithic silica gels dotted with axially
substituted phthalocyanine of Zr(IV), Hf(IV) and selected lanthanides.
Yuriy Gerasymchuk*, Victor Chernii**, Larisa Tomachynski**, Irina Tretyakova**, Janina Legendziewicz*, Stanisław Radzki***
* Faculty of Chemistry, Wrocław University, 14 F. Joliot-Curie str., 50-383 Wrocław, Poland
**V.I.Vernadskii Institute of General and Inorganic Chemistry, 32/34 Palladin ave., Kiev, Ukraine.
*** Faculty of Chemistry, Maria Curie-Skłodowska University, 20-031 Lublin, Poland
General properties and applies of phthalocyanine dotted sol-gel materials
For over 30 years phthalocyanine dyes have been extensively studied due to their spectroscopic and photoelectric properties and can be applied in many branches:
in the field of physics, in technique, medicine, chemistry and other sciences. Metallophthalocyanine compounds have attracted special attention due to their unique
properties such as conductivity electrochromism and variety of catalytic function. Phthalocyanines are characterized by significant absorption in the visible region,
large absorption coefficient, and high thermal and photochemical stability. For that reason they are good potential candidates in solar-to-electric energy conversion
and as modulators of light energy in laser devices. As model system for phthalocyanine basic solar-to-electric energy converters, optical data carriers, chemical
sensors and laser devices we can use sol-gel materials doped by metalloporphyrins and its analogues – metalophthalocyanines. It is a new mixing organic and
inorganic hybrid material with unique physical, chemical and optical properties. Sol-gel monolith and sol-gel thin films are very useful to encapsulate various guests
such as inorganic clusters, lanthanide complexes, laser dyes etc. Different complexes including metalloporphyrin and metallophthalocyanine based systems have
also been encapsulated by sol-gel processing to give hybrid organic-inorganic. Application of the metalroporphyrins and metalophthalocyanines dotted sol-gel
materials as catalyst of oxidation of alkenes, aromatic, halogenoorganic and other organic and inorganic compounds have been also reported. Moreover, sol-gel
materials have been intensively investigated as host media to encapsulate different spacious biological materials, including enzymes, catalytic antibodies, proteins,
polynucleic acids, microbials, animal cells and plants for applications in byocatalysis, immunodiagnostics, bioptical devices and as biosensors or bioimplants.
Types of investigated axially substituted phthalocyanatometal complexes and solubility
Group I
Group II
Group III
M(IV) = Zr, Hf
M(IV) = Zr, Hf
L = gallic acid; 5-sulfosalicylic acid; oxalic acid,
methyl ester of gallic acid
L = 2,4-pentanedione, pirocatecholic acid,
citric acid
Soluble in water and most of polar organic
solvents
Soluble in benzene, toluene, pyridine, THF
M(IV) = Dy, Ho, Er, Tm, Yb, Lu
Introduction of substituents to the peripheral position of Pc macrocycle is
known to influence significantly the physical and chemical properties of PcM
system. Moreover, metallophthalocyanine complexes containing metal in
valence higher than two give possibility to bind directly to the metal one or
more additional ligands, usually in the so called out of plane position,
perpendicular to the N8 moiety. The axial ligands can significantly change the
spectral, photophysical and other properties of PcM complexes. The mixed
ligand phthalocyanine compounds are also good substrates for the synthesis
even more complicated sandwich-type or trinuclear complexes.
Soluble in pyridine, DMSO, DMF
Standard method of obtaining of gels, dotted by phthalocyanines of I and II groups of investigated complexes
The alcogels with various amounts of complexes from group I and II were synthesized by standard
method: the sol-gel polymerization of tetraethyl orthosilicate [Si(OC2H5)4 - TEOS]. HCl was used as
hydrolysis catalyst and NH3 aq. as a condensation catalyst to synthesize TEOS alcogels. We mixed
TEOS (65%) with distilled water (35%) and HCl. After hydrolysis, we added NH3 aq. to the TEOS mixture.
Mixture was doped with DMSO solutions of group I complexes [2·10^-4 M/dcm3] and THF/DMSO=1:1
solutions of group II complexes, for achieving of concentration of phthalocyanines in alcogels of the
order of 2.5·10^-4 – 4·10^-5 M/dcm^3. We was not added formamide as antycracking reagent to mixture,
because DMSO fulfilled the same function. Then, the sol was gelled in disposal polyacrylic cells sealed
with parafilm to mesure light absorption before and after gelation. Final gelation was achieved after 3
days. After month parafilm was perforated to allow evaporate pore solvent during monolith drying. The
following percent ratio was used: TEOS:H2O=65:35. Amount of DMSO was responded of the amount of
added solution of phthalocyanine complexes. Gels with largest DMSO content has a longer time of
gelation and drying.
Preparation of transparent monolithic silica gels, dotted by lanthanide containing axially substituted phthalocyanines
The aceto- substituted phthalocyanines of lanthanides have several of negative properties in point of view of dotting of silica gels with using of
standard method, described above. First o all, the complexes of lanthanides from Ce to Eu have a very bad solubility in most of organic solvents,
used for gel dotting. On the other side, that complexes are demetalized in presence of light alcohols ( such as methanol, ethanol, propanol or
izopropanol), that are liberate in time of hydrolysation and poly-condensation of silica gel precursors. But they are relatively stable in butanol (we
checked the line of alcohols respectively tu commercial precursors). We evolved a new method of obtaining of transparent monolithic silica gel
with using of tetrabutylorthosilicate as pecursor. A solution, mixed in mole ratios, of tetrabutyl orthosilicate (C4H9O)4Si : n-butyl alcohol : water :
HCl = 350:150:10:1 was heated and stirred at a temperature of 120° C for three hours, whereby the solution used for a sol-gel method was
synthesized. After cooling, the appropriate amount of complex solution in DMSO was added with stirring.
Just after
gel formation
Dried, after month
Dried, after year
Absorption properties of investigated axially substituted phthalocyanatometal complexes incorporated in silica gels
0.8
1.2
Before gelling
After gelling
After one month drying
After one year drying
EtOH solution
H2O solution
A
0.6
Cm=2*10-5
Cm=1*10-5
-6
Cm=5*10
Cm=2.5*10-6
A
1.0
The phthalocyanines encapsulated in silica matrixes shows specific spectral characteristics. However at first glance the absorption characteristic
of these complexes in silica gels is similar to that one in solutions, detailed analysis shows many differences. The most important is conclusion
that molecules of investigated complexes of phthalocyanines in gels exist not only in solution closed in the micro pores of matrix, but also in the
form of extra complexes, formed by direct phthalocyanines bonds with silica matrix. The changes in spectral properties of zirconium and hafnium
phthalocyanine complexes depend on the stage of sol to gel to glass pathway. Aggregation processes, and their dependence upon concentration
of complexes and stages of forming of silica matrix have been also described.
0.8
DMSO solution
0.6
0.4
0.4
0.2
0.2
0.0
0.0
300
400
500
600
700
nm
800
a)
300
400
500
600
700
800
900
nm
Excitation and emission properties of investigated phthalocyaine complexes incorporated in silica gels
6e+5
-6
Cm = 2.5*10
-6
Cm = 5*10
-5
Cm = 1*10
-5
Cm = 2*10
Undotted gel
det= 500nm
1.5e+5
1.0e+5
5.0e+4
0.0
300
350
400
450
 [nm]
500
80000
Cm = 2.5*10-6
-6
Cm = 5*10
-5
Cm = 1*10
Cm = 2*10-5
Relative intensity
60000
det= 750-765nm
40000
Comparing the excitation and emission spectra in solution and glassy solid matrix much more differences
than in absorption spectra can be notices. This is from the one side result of the stronger phthalocyanine
aggregation in the pores of dry gel and dry and concentration quenching effect, from the second side the
Soret band overlaps with strong emission band of silica matrix. The last effect disappears when
phthalocyanine in solid are excited by the wavelengths longer than 550 nm.
It must be also emphasised that due to the intensive 700-725 nm emission upon relatively long wavelength
excitation the axially substituted zirconium and hafnium phthalocyanines can be considered as
photodynamic therapy agents, which might be selective towards the certain types of tumour cells. The
successful incorporation into silica gels proved that fibber optics dotted by investigated phthalocyanines
could be used in photodynamic therapy. This type of fibber optics when providing 630 nm light would
excite addition emission about 710 nm. Special fibber can be prepared either in the monolithic form or
silica fibber could be covered by the sol-gel thin film containing investigated phthalocyanines.
20000
0
300
400
500
600
nm 700
-6
Relative intensity of fluorescence
Relative intensity
2.0e+5
3e+5
ex = 400nm
2e+5
1e+5
Cm = 2.5*10
-6
Cm = 5*10
Cm = 1*10-5
Cm = 2*10-5
5e+5
4e+5
ex = 620nm
3e+5
2e+5
1e+5
0
0
300
400
500
700  [nm] 800
600
660
680
700
720
740
760
50000
Relative intensity of fluorescence
Cm = 2.5*10-6
-6
Cm = 5*10
-5
Cm = 1*10
Cm = 2*10-5
Relative intensity of fluorescence
2.5e+5
Cm = 2.5*10
-6
Cm = 5*10
-5
Cm = 1*10
-5
Cm = 2*10
40000
-6
30000
20000
10000
0
500
600
700
800
 [nm]
900
AFM pictures and computer analysis of surfaces of obtained phthalocyanine dotted silica gels
The using of computer analysis of AFM pictures, that was registered for silica gels, gives ability to make
several basic conclusions:
100nm
100nm
• The surface of “free” undotted solica gels, that was obtained by hydrolysis and
polycondensation of precursors (TEOS, TBOS) is much smooth than non modified
surfaces of metals. Their “roughness” is comparable with glass surface.
• The ”smooth” surface of silica gels is the perfect medium for immobilization and
visualization (representation on surface) the porphyrine and phthalocyanine molecules by
using of AFM method.
• The agglomeration processes of axially substituted phthalocyanine complexes of Zr(IV)
and Hf(IV) can be estimated directly from AFM pictures by using the fractal analysis of
pictures.
780
800
 [nm]