Synthesis and spectral properties of Zr(IV) and Hf(IV) phthalocyanines with β-diketonates as axial ligands

Article abstract of DOI:10.1016/j.ica.2007.11.003

The series of new zirconium(IV) and hafnium(IV) phthalocyanines with various β-dicarbonyl ligands were prepared via direct interaction between di(chloro)zirconium(IV) or hafnium(IV) phthalocyanines and free β-diketones and also with 4-benzoyl-3-methyl-1-p

Full text of DOI:10.1016/j.ica.2007.11.003

Available online at www.sciencedirect.com
Inorganica Chimica Acta 361 (2008) 2569–2581
www.elsevier.com/locate/ica
Review
Synthesis and spectral properties of Zr(IV) and Hf(IV)
phthalocyanines with b-diketonates as axial ligands
a
a
a
a
b
L.A. Tomachynski , I.N. Tretyakova , V.Ya. Chernii , S.V. Volkov , M. Kowalska ,
b
c,
c
J. Legendziewicz , Y.S. Gerasymchuk *, St. Radzki
a
Institute of General and Inorganic Chemistry, Prospect Palladina 32/34, Kiev, Ukraine
b
Faculty of Chemistry, Wrocław University, F. Joliot-Curie 14, 50-383 Wrocław, Poland
Faculty of Chemistry, M. Curie-Skłodowska University, M.C-S. Sq. 2, 20-031 Lublin, Poland
c
Received 21 February 2007; received in revised form 17 July 2007; accepted 2 November 2007
Available online 7 November 2007
Abstract
The series of new zirconium(IV) and hafnium(IV) phthalocyanines with various b-dicarbonyl ligands were prepared via direct inter-
action between di(chloro)zirconium(IV) or hafnium(IV) phthalocyanines and free b-diketones and also with 4-benzoyl-3-methyl-1-phe-
nyl-2-pyrazolin-5-one. The structure of the obtained bis(b-dicarbonilato) zirconium(IV) and hafnium(IV) phthalocyanines was studied
1
by two dimension H NMR spectroscopy (COSY, NOESY, ROESY). Absorption and fluorescence spectroscopic studies have been
investigated in various solvents. Analyzed compounds of concentration range below 10ꢀ5 mol/dm3 do not aggregate in the organic sol-
vents. Fluorescence quantum yields (UF) and natural life times (s) of zirconium phthalocyanine complexes have been calculated in tol-
uene, DMSO and THF.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Phthalocyanine; Zirconium(IV); Hafnium(IV); b-Diketones; 2D NMR spectroscopy; Electronic absorption and emission spectra; Fluorescence
Iryna N. Tretyakova has done her Master’s
Larisa A. Tomachynski has done her Master’s
degree in Chemistry-Biology in the Faculty of
degree in Chemistry, Chemical Faculty of
Chemistry and Biology of the State Pedagog-
Taras Shevchenko National University (Kyiv,
ical Institute (Melitopol, Ukraine) in the year
Ukraine) in the year 1991. During 1998–2001,
1984. Since 1986, she has been working at
she was the PhD student at V.I.Vernadskii
V.I.Vernadskii Institute of General and Inor-
Institute of General and Inorganic Chemistry
ganic Chemistry NAS of Ukraine (Kyiv,
NAS of Ukraine (Kyiv, Ukraine). In 2002 she
Ukraine). In 2007 she did her PhD at
did her PhD at V.I.Vernadskii Institute of
V.I.Vernadskii Institute of General and Inor-
General and Inorganic Chemistry (Kyiv,
ganic Chemistry (Kyiv, Ukraine).
Ukraine). Since 2002, she has been holding a
scientific researcher at the same Institute.
*
Corresponding author. Tel.: +48 81 537 5749.
E-mail address: gerasymchuk@vip-inter.com (Y.S. Gerasymchuk).
0020-1693/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.11.003

2570
L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
referees panels of Journal of Physics-Condensed Matter, Spectrochimica
Viktor Ya. Chernii has done her Master’s degree in
Chemistry, Chemical Faculty of Taras Shevchenko
National University (Kyiv, Ukraine) in the year
1993. During 1993–1996, he was the PhD student
at V.I.Vernadskii Institute of General and Inor-
ganic Chemistry NAS of Ukraine (Kyiv, Ukraine).
In 1998 he did his PhD at V.I.Vernadskii Institute
of General and Inorganic Chemistry (Kyiv,
Ukraine). Since 2006, he has been holding a senior
scientific researcher at the same Institute.
Acta, New Journal of Chemistry, Journal of Alloys and Compounds, PCCP,
Optical Materials, J. Luminescence, Phys. Chem. Phys., Inorganica Chi-
mica Acta and others. Deputy Director of the Institute of Chemistry,
Wroclaw University (1990–1993).
Y.S. Gerasymchuk had done his Bachelor’s degree
in Biology, Bioorganic Chemistry Division, Faculty
of Natural Sciences of National University ‘‘Kyiv-
Mohyla Akademy’’ (Kiyv, Ukraine) in the year
1999. In 2001, he did his Master’s degree in Biol-
ogy, at the National Univesity ‘‘Kyiv-Mohyla
Akademy’’ (Kyiv, Ukraine). During 2001–2005, he
was a participant of European Collegium of Polish
and Ukrainian Universities. In 2005, he did his
PhD at the Faculty of Chemistry of Marie Curie-
Skłodowska University (Lublin, Poland). Since
2006, he has been holding a postdoctoral position at the Faculty of Chem-
istry, Wroclaw University (Wrocław, Poland).
Sergey V. Volkov. he finished the Faculty of
Physical Chemistry of the D.I. Mendeleev Institute
of Chemical Engineering in Moscow in 1959. In
1960 he moved to Kiev to the Institute of General
and Inorganic Chemistry of the Academy of Sci-
ences of Ukraine (IGIC-ASU). In 1964 he did his
PhD and in 1974 he defended his DrSc thesis at
IGIC-ASU (Kyiv, Ukraine). In 1975 he organized
the Laboratory of High-Temperature Inorganic
Chemistry at the IGIC-ASU. In November 1992,
he was elected as an Academician of the National
Academy of Sciences of Ukraine. Since 1992, S.V.Volkov has been holding
the director of V.I.Vernadskii Institute of General and Inorganic Chemistry
of NAS (Kyiv, Ukraine).
Stanislaw Pawel RADZKI, M.Sc. 1972 (Faculty
of Mat-Phys-Chem); Ph.D. 1980 (Faculty of
Chemistry), since 1995 Professor Inorganic and
Bioinorganic Chemistry at Faculty of Chemistry
(M.Curie-Sklodowska
Poland).
University,
Lublin,
Postdoc Fellow: Centre National de la Recherche´
Scientifique, Institute de Chimie des Substances
Naturelles, Gif-sur-Yvette, France (1985/1986)
Research Fellow: Center for the Chemical Physics,
Western Ontario University, London, Canada,
Janina Legendziewicz M.Sc. 1961, Ph.D. 1971,
D.Sc. 1987, Prof. 1994 Head of a Research Group
Physical Chemistry of Lanthanides and Structure
of Liquid Systems University of Wrocław. Member
of European Union panel of NEST science program
(1990/1991).
and reviewer of European scientific projects.
Member of the Polish Chemical Society, European
Visiting Professor: Centre National de la Recherche´ Scientifique, Institute
de Chimie des Substances Naturelles, Gif-sur-Yvette, France (1991/1992).
Visiting Professor: Faculte´ de Sciences, The University of Limoges, Limo-
ges, France, (1992, 1993, 1994, 2001, 2003 every time 6 weeks).
Research areas: Synthesis and physico-chemical properties of metal com-
plexes with porphyrins and phthalocyanines; Interaction of free-base por-
phyrins and their metal complexes with proteins and compounds of biological
importance; Sol-gel technology.
Rare Earth and Actinides Society, Molecular
Medicine Society. Member of the Spectroscopic
Committee of the Polish Academy of Sciences until
its dissolution (1990). Member of the Theory and
Structure of Molecular and Condensed Systems Commission of the Wrocław
Branch of the Polish Academy of Sciences. Member of the Analytical
Chemistry Committee, Polish Academy of Sciences (Commission of Edu-
cation). Member of the editorial board of Materials Science. Member of the
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2571
2. Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2571
2.1. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2571
2.2. Spectral measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2571
2.3. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2572
2.3.1. Synthesis of dichloro(chlorinephthalocyaninato) zirconium(IV) (Pc(Cl)ZrCl2) (I). . . . . . . . . . . . . . . . . . . 2572
2.3.2. Synthesis of dichloro(chlorinephthalocyaninato) hafnium(IV) (Pc(Cl)HfCl2) (II) . . . . . . . . . . . . . . . . . . . 2572
2.3.3. Synthesis of dichloro(phthalocyaninato) zirconium(IV) (PcZrCl2) (III) . . . . . . . . . . . . . . . . . . . . . . . . . . 2572
2.3.4. Synthesis of dichloro(phthalocyaninato) hafnium(IV) (PcHfCl2) (IV) . . . . . . . . . . . . . . . . . . . . . . . . . . . 2573
2.3.5. Synthesis of bis(2,4-pentanedionato)zirconium(IV) chlorinephthalocyanine (V) . . . . . . . . . . . . . . . . . . . . 2573
2.3.6. Synthesis of bis(2,4-pentanedionato)hafnium(IV) chlorinephthalocyanine (VI). . . . . . . . . . . . . . . . . . . . . 2574
2.3.7. Synthesis of bis(2,4-pentanedionato)zirconium(IV) phthalocyanine (VII). . . . . . . . . . . . . . . . . . . . . . . . . 2574

L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
2571
2.3.8. Synthesis of bis(2,4-pentanedionato)hafnium(IV) phthalocyanine (VIII) . . . . . . . . . . . . . . . . . . . . . . . . . 2574
2.3.9. Synthesis of bis(2,4-decanedionato)zirconium(IV) phthalocyanine (IX) . . . . . . . . . . . . . . . . . . . . . . . . . . 2575
2.3.10. Synthesis of bis(2,4-decanedionato)hafnium(IV) phthalocyanine (X) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2575
2.3.11. Synthesis of bis(2-methoxy-2,6,6-trimethyl-3,5-heptanedionato)zirconium(IV) phthalocyanine (XI) . . . . . . 2575
2.3.12. Synthesis of bis(2-methoxy-2,6,6-trimethyl-3,5-heptanedionato)hafnium(IV) phthalocyanine (XII) . . . . . . 2575
2.3.13. Synthesis of bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)zirconium(IV) phthalocyanine (XIII). . . . . . . . 2575
2.3.14. Synthesis of bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)hafnium(IV) phthalocyanine (XIV) . . . . . . . . . 2575
2.3.15. Synthesis of bis(1-phenyl-4,4,4-trifluoro-1,3-butanedionato)zirconium(IV) phthalocyanine (XV) . . . . . . . . 2575
2.3.16. Synthesis of bis(1-phenyl-4,4,4-trifluoro-1,3-butanedionato)hafnium(IV) phthalocyanine (XVI) . . . . . . . . 2576
2.3.17. Synthesis of bis(1-phenyl-1,3-butanedionato)zirconium(IV) phthalocyanine (XVII) . . . . . . . . . . . . . . . . . 2576
2.3.18. Synthesis of bis(1-phenyl-1,3-butanedionato)hafnium(IV) phthalocyanine (XVIII) . . . . . . . . . . . . . . . . . . 2576
2.3.19. Synthesis of N1-(4-metoxyphenyl)-2-(1-acetyl-2-oxopropylsulfanyl)acetamide . . . . . . . . . . . . . . . . . . . . . 2576
2.3.20. Synthesis of bis(N1-(4-metoxyphenyl)-2-(1-acetyl-2-oxopropylsulfanyl)acetamido) zirconium(IV)
phthalocyanine (XIX). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2576
2.3.21. Synthesis of bis(N1-(4-metoxyphenyl)-2-(1-acetyl-2-oxopropylsulfanyl)acetamido) hafnium(IV)
phthalocyanine (XX) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2576
2.3.22. Synthesis of bis(4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-onato)zirconium(IV) phthalocyanine (XXI) . . 2577
2.3.23. Synthesis of bis(4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-onato)hafnium(IV) phthalocyanine (XXII) . . . 2577
3. Results and discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2577
3.1. Luminescence properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2578
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2581
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2581
1. Introduction
NMR spectroscopy (COSY, NOESY and ROESY). Sum-
marizing all data of 2D H NMR spectroscopy we can
1
Metallophthalocyanines due to their unique electronic
structure display interesting spectroscopic and photoelec-
tric properties, which have been extensively studied for
many years, firstly because of their classical use as dyes.
Recently, the increasing attention to metallophthalocya-
nine complexes is result of their applications in modern
technology. Their unique properties such as conductivity,
electrochromism or variety of catalytic functions, make
them ideal compounds for applications as electrochromic
materials [1], photoconductors [2], sensors [3] and for the
other advanced applications [4]. Although phthalocya-
nines, with some exceptions, are considered to be toxic,
they find application in medicine, as photosensitizers in
PDT (photodynamic therapy) [5–8].
establish the structure of the synthesized mixed ligand
dicarbonilato and phthalocyanine complexes with rela-
tively high precision. Their spectral luminescent properties
were also investigated.
2. Experimental
2.1. Materials
Zirconium and hafnium tetrachloride, phthalodinitrile,
2-methylnaphthalene, 2,4-pentandione, 1-phenyl-1,3-butane-
dione,
4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one,
3-chloro-2,4-pentandione were purchased from Aldrich
and used as received. 1,2,4-Trichlorobenzene, toluene,
hexane, and CHCl3 and all other organic solvents were
of reagent grade and were used without further purification.
Introduction of the substituents to the peripheral posi-
tion of Pc macrocycle change significantly the physical
and chemical properties of the PcM system [9–11]. More-
over, metallophthalocyanine complexes containing metal
in valence state higher than two give the possibility to bind
directly to the metal one or more additional ligands, usually
in so-called out of plane position, perpendicular to the N8
moiety. The axial ligands can significantly change the spec-
tral, photophysical and other properties of PcM complexes
[12–17]. The mixed ligand phthalocyanine compounds are
also good substrates for the synthesis even more compli-
cated sandwich-type or trinuclear complexes [18–20].
We report in this work the synthesis of the axially substi-
tuted zirconium(IV) and hafnium(IV) phthalocyanines. We
also concern on the determination of the structure of
obtained mixed ligands bis(b-dicarbonilato)zirconium(IV)
2.2. Spectral measurements
Measurements of the electronic absorption spectra were
carried out at room temperature using a Carl-Zeiss, Jena,
Specord M-40 spectrometer. The UV–Vis spectra of the ana-
lyzed mixed ligand complexes were recorded in CHCl3 solu-
tions (c = 10ꢀ6 mol/dm3, l = 1 cm). IR spectra were
recorded on a Carl-Zeiss, Jena, Specord M-80 spectrometer
in KBr (FT-IR grade, Aldrich) disks. Steady-state fluores-
cence spectra were collected with a spectrofluorimeter
Hitachi 1200 in toluene, DMSO and THF (c = 10ꢀ6 mol/
dm3, l = 1 cm). A Carl-Zeiss (Jena) refractometer Abbe type
was used for the determination the refractive indexes of the
phthalocyanine solutions (c = 10ꢀ6 mol/dm3).
1
and hafnium(IV) phthalocyanine complexes by the 2D H

2572
L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
1H NMR spectra were obtained with a Bruker NMR
Avance spectrometer operating in a quadrature mode at
500 MHz (500) NMR spectrometer.
tion, the suspension was cooled to 50 ꢁC and filtered.
The precipitate was washed with benzene and methanol
until washings were no longer colored and finally air-dried
at room temperature. Yield: 71%. Anal. Calc. for
C32H15Cl3N8Zr: C, 54.20; H, 2.13; N, 15.80; Zr, 12.86.
Found: C, 54.50; H, 2.50; N, 15.45; Zr, 12.50%. IR
(KBr, cmꢀ1): 1685 (w), 1605 (w), 1500 (m), 1465 (w),
1415 (m), 1385 (w), 1330 (s), 1310 (w), 1285 (s), 1155
(m), 1115 (s), 1070 (s), 1050 (s), 1010 (m), 950 (w), 890
(s), 870 (w), 825 (m), 790 (m), 765 (m), 745 (s), 730 (s),
630 (w), 565 (w), 500 (m), 430 (m), 345 (m), [masym(Zr–
Cl)], 315 (s) [msym(Zr–Cl)].
2.3. Synthesis
Synthesis of dichloro(chlorine)- and dichlorophthalocy-
anines of zirconium(IV) and hafnium(IV) is shown in
Scheme 1. The same reaction but without 2-methylnaph-
thalene, results in chlorination of one benzene ring in the
phthalocyanine plane. The presence of 2-methylnaphtha-
lene, avoid the chlorination of the Pc ring inasmuch 2-
methylnaphthalene is an easy-chlorinated reagent and
‘‘remove’’ free chlorine radical which usually chlorinate
phthalonitrile during tetramization or formed Pc macrocy-
cle. The products of 2-methylnaphthalene chlorination can
be easy removed from reaction mixture. Hanack et al. [21]
prepared axially substituted tetrapyrazinotetraazaporphyr-
inatotitanoin(IV) oxides. Trying to avoid the complex
hydrolysis we applied different condition of the synthesis,
as high boiling solvent. In these conditions we do not
obtain neither Pc(Zr/Hf)O nor Pc(Zr/Hf)M(OH) [22].
Zirconium and hafnium dichlorophthalocyanines were
treated as starting materials for the synthesis of other
mixed ligand complexes shown in Schemes 1–3. All reac-
tions were carried out under atmospheric conditions.
Details about complex preparation are described below.
2.3.2. Synthesis of dichloro(chlorinephthalocyaninato)
hafnium(IV) (Pc(Cl)HfCl2) (II)
It was prepared from hafnium tetrachloride by the
same procedure as (I). Yield: 77%. Anal. Calc. for
C32H15Cl3N8Hf: C, 48.26; H, 1.90; N, 14.07; Hf, 22.41.
Found: C, 48.50; H, 2.00; N, 13.90; Hf, 22.50%. IR
(KBr, cmꢀ1): 1605 (w), 1500 (m), 1465 (m), 1415 (m),
1385 (w), 1330 (s), 1285 (s), 1155 (m), 1115 (s), 1070
(s), 1050 (s), 1005 (m), 945 (w), 890 (s), 870 (w), 825
(m), 790 (m), 765 (m), 745 (s), 730 (s), 625 (w), 565
(w), 500 (m), 430 (m), 300 (s) [masym(Hf–Cl)], 285 (m)
[msym(Hf–Cl)].
2.3.3. Synthesis of dichloro(phthalocyaninato) zirconium(IV)
(PcZrCl2) (III)
2.3.1. Synthesis of dichloro(chlorinephthalocyaninato)
zirconium(IV) (Pc(Cl)ZrCl2) (I)
Phthalodinitrile (0.1 mol) was dissolved in 15 ml of hot
1,2,4-trichlorobenzene, then 0.025 mol of zirconium tetra-
chloride was added to the solution. The reaction mixture
was heated at 220 ꢁC for 1 h. After completing the reac-
Phthalodinitrile (0.1 mol) and 2-methylnaphthalene
(0.025 mol) were dissolved in 15 ml of hot 1,2,4-trichloro-
benzene and 0.025 mol of zirconium tetrachloride was
added to solution, then the reaction mixture was heated
at 220 ꢁC for 1 h. After completing the reaction, the sus-
Cl
Cl
M
CH
3
N+
N
N+
N
N
170-2300C
N
N
N
CN
CN
(III, IV)
MCl4
+
4
Cl
M
Cl
Cl
2200C
Cl
Cl
N+
N
N+
N
N
N
N
N
Cl
M = Zr(IV), Hf(IV)
(I, II)
+
O
O
CH
1160C
3
O
O
N
O
O
M
N
N
N
N
N
N
N
(V, VI)
Scheme 1.
Cl

L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
2573
O
O
N
O
O
M
N
N
N
N
N
N
N
(VII, VIII)
O
O
O
O
O
O
O
O
M
Cl
Cl
N
N
N
M
N
N
N
N
N+
N
N
N+
N
N
N
O
(IX, X)
N
N
O
F
O
O
O
O
O
O
O
M
F
F
N
F
F
N
N
F
N
N
N
N
O
O
N
(XI, XII)
M = Zr(IV), Hf(IV)
F
F
F
F
F
F
F
F
F
F
F
F
O
O
O
O
M
N
N
N
N
N
N
N
N
(XIII, XIV)
Scheme 2.
pension was cooled to 50 ꢁC and filtered. The precipitate
was washed with benzene and methanol until washings
were no longer colored and finally air-dried at room tem-
perature. Yield: 73%. Anal. Calc. for C32H16Cl2N8Zr: C,
56.97; H, 2.39; N, 16.61; Zr, 13.52. Found: C, 56.80; H,
2.50; N, 16.20; Zr, 13.50%. IR (KBr, cmꢀ1): 1685 (w),
1605 (w), 1500 (m), 1465 (w), 1415 (m), 1385 (w), 1330
(s), 1310 (w), 1285 (s), 1155 (m), 1115 (s), 1070 (s), 1050
(s), 950 (w), 890 (s), 870 (w), 825 (m), 790 (m), 765 (m),
745 (s), 730 (s), 630 (w), 565 (w), 500 (m), 430 (m), 345
(m) [masym(Zr–Cl)], 315 (s) [msym(Zr–Cl)].
945 (w), 890 (s), 870 (w), 825 (m), 790 (m), 765 (m), 745
(s), 730 (s), 625 (w), 565 (w), 500 (m), 430 (m), 300 (s)
[masym(Hf–Cl)], 285 (m) [msym(Hf–Cl)].
2.3.5. Synthesis of bis(2,4-pentanedionato)zirconium(IV)
chlorinephthalocyanine (V)
A 0.74 mmol of Pc(Cl)ZrCl2 was suspended in 10 ml of
toluene and 1.67 mmol 2,4-pentandione was added to the
suspension. The reaction mixture was heated at 116 ꢁ C
for 4 h under reflux (evolution of HCl was observed). Then
the hot reaction mixture was filtered and the obtained solu-
tion was cooled to room temperature. The formed crystals
of bis(2,4-pentadionato)phthalocyanine complex of zirco-
nium were separated and washed abundantly with hexane.
Hexane was added to the remaining solution what caused
an additional crystallization of the final product. The
resulting precipitates were collected and dried, firstly in
the air and finally in a vacuum at 60 ꢁC for 8 h. Anal. Calc.
for C42H29ClN8O4Zr: C, 60.31; H, 3.49; N, 13.40; Zr,
10.91. Found: C, 59.90; H, 3.50; N, 13.10; Zr, 10.50%.
2.3.4. Synthesis of dichloro(phthalocyaninato) hafnium(IV)
(PcHfCl2) (IV)
It was prepared from hafnium tetrachloride by the same
procedure as (III). Yield: 76%. Anal. Calc. for
C32H16Cl2N8Hf: C, 50.44; H, 2.12; N, 14.71; Hf, 23.43.
Found: C, 50.50; H 2.00; N, 14.50; Hf, 23.50%. (KBr,
cmꢀ1): 1605 (w), 1500 (m), 1465 (m), 1415 (m), 1385 (w),
1330 (s), 1285 (s), 1155 (m), 1115 (s), 1070 (s), 1050 (s),

2574
L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
F
F
F
F
F
F
O
O
N
O
F
F
O
M
F
N
N
N
N
O
N
N
O
N
(XV, XVI)
O
O
N
O
Cl
Cl
O
M
O
O
M
N
N
N
N
N+
N
N
N+
N
N
N
N
N
N
N
O
(XVII, XVIII)
O
S
O
O
O
O
N
N
N
O
O
S
S
O
N
O
O
N
O
O
O
M
N
N
N
N
N
N
N
N
(XIX, XX)
N
M = Zr(IV), Hf(IV)
N
O
N
N
O
O
M
O
N
N
N
N
N
N
N
N
(XXI, XXII)
Scheme 3.
IR (KBr, cmꢀ1): 2950–2940 (w), 1600 (s), 1575 (s), 1540 (s),
1510 (s), 1468 (m), 1420 (m), 1387 (m), 1360 (m), 1335 (s),
1288 (s), 1164 (m), 1120 (s), 1080 (sh), 1070 (s), 1032 (m),
1008 (m), 898 (m), 830 (m), 825 (sh), 780 (s), 755 (s), 743
(s), 460 (m), 450 (m).
2.3.7. Synthesis of bis(2,4-pentanedionato)zirconium(IV)
phthalocyanine (VII)
It was prepared from PcZrCl2 and 2,4-pentandione by
the same procedure as (V). Yield:64%. Anal. Calc. for
C42H30N8O4Zr: C, 62.90; H, 3.77; N, 13.97; Zr, 11.37.
Found: C, 62.50; H, 3.75; N, 13.45; Zr, 11.52%. IR (KBr,
cmꢀ1): 2950–2940 (w), 1600 (s), 1575 (s), 1540 (s), 1510
(s), 1468 (m), 1420 (m), 1387 (m), 1360 (m), 1335 (s), 1288
(s), 1164 (m), 1120 (s), 1080 (sh), 1070 (s), 1032 (m), 898
(m), 830 (m), 825(sh), 780 (s), 755 (s), 743 (s), 460 (m),
2.3.6. Synthesis of bis(2,4-pentanedionato)hafnium(IV)
chlorinephthalocyanine (VI)
It was prepared from Pc(Cl)HfCl2 and 2,4-pentandione
by the same procedure as (V). Yield: 44%. Anal. Calc. for
C42H29ClN8O4Hf: C, 54.61; H, 3.16; N, 12.13; Hf, 19.32;
Found: C, 54.50; H, 3.00; N, 11.90; Hf, 19.50%. IR
(KBr, cmꢀ1): 2960–2920 (w), 1610 (s), 1575 (s), 1540 (s),
1510 (s), 1468 (m), 1420 (m), 1390 (s), 1335 (s), 1288 (s),
1164 (m), 1120 (s), 1080 (sh), 1070 (s), 1030 (m), 1000
(m), 898 (m), 830 (m), 825 (sh), 780 (s), 755 (s), 743 (s),
440 (m), 420 (m).
1
450 (m). H NMR (d ppm, CDCl3): 9.46 (8H, m, Ha);
8.16 (8H, m, Hb); 4.25 (2H, s, 2CH); 1.23 (12H, s, 4CH3).
2.3.8. Synthesis of bis(2,4-pentanedionato)hafnium(IV)
phthalocyanine (VIII)
It was prepared from PcHfCl2 and 2,4-pentandione by
the same procedure as (V). Yield: 66%. Anal. Calc. for

L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
2575
C42H30N8O4Hf: C, 56.73; H, 3.40; N, 12.60; Hf, 20.07.
Found: C, 56.60; H, 3.20; N, 12.10; Hf, 20.10%. IR
(KBr, cmꢀ1): 2960–2920 (w), 1610 (s), 1575 (s), 1540 (s),
1510 (s), 1468 (m), 1420 (m), 1390 (s), 1335 (s), 1288 (s),
1164 (m), 1120 (s), 1080 (sh), 1070 (s), 1030 (m), 898 (m),
830 (m), 825 (sh), 780 (s), 755 (s), 743 (s), 440 (m), 420
2.3.12. Synthesis of bis(2-methoxy-2,6,6-trimethyl-3,5-hep-
tanedionato)hafnium(IV) phthalocyanine (XII)
It was prepared from PcHfCl2 and 2-methoxy-2,6,6-tri-
methyl-3,5-heptanedione by the same procedure as (V).
Yield: 49%. Anal. Calc. for C54H54N8O6Hf: C, 59.53; H,
5.00; N, 10.28; Hf, 16.38. Found: C, 59.20; H 5.15; N,
10.05; Hf, 16.55%. (KBr, cmꢀ1): 2940 (m), 1605 (sh),
1590 (s), 1568 (s), 1550 (sh), 1509 (s), 1499 (sh), 1465m,
1455 (sh), 1420 (m), 1405 (m), 1390 (m), 1360 (m), 1330
(s), 1290 (s), 1230 (m), 1175 (m), 1160 (m), 1118 (s), 1082
(sh), 1070 (s), 1050 (m), 960 (m), 938 (m), 900 (m), 825
(m), 820 (sh), 775 (m), 765 (m), 750 (s), 740 (s), 735 (s),
1
(m). H NMR (d ppm, CDCl3): 9.17 (8H, m, Ha); 8.10
(8H, m, Hb); 4.60 (2H, s, 2CH); 1.19 (12H, s, 4CH3).
2.3.9. Synthesis of bis(2,4-decanedionato)zirconium(IV)
phthalocyanine (IX)
It was prepared from PcZrCl2 and 2,4-decandione by the
same procedure as (V). Yield: 49%. Anal. Calc. for
C52H50N8O4Zr: C, 66.29; H, 5.35; N, 11.89; Zr, 9.68.
Found: C, 66.50; H, 5.10; N, 11.40; Zr, 9.50%. IR (KBr,
cmꢀ1): 2960 (m), 2930 (m), 2860 (m), 1602 (s), 1592 (s),
1575 (s), 1567 (sh), 1531 (s), 1505 (s), 1467 (m), 1420 (m),
1400 (m), 1365 (sh), 1335 (s), 1285 (s), 1162 (m), 1120 (s),
1075 (s), 1050 (sh), 900 (m), 825 (m), 780 (m), 770 (m),
750 (s), 740 (s), 1420 (m), 1335 (s), 1285 (s), 1162 (m),
1120 (s), 1075 (s), 1050 (sh), 900 (m), 780 (m), 770 (m),
750 (s), 740 (s), 440 (m), 430 (sh). 1H NMR (d ppm, CDCl3):
9.43 (8H, m, Ha); 8.12 (8H, m, Hb); 4.19 (2H, d, 2CH); 1.54;
1.28 (4H, m, 2CH2); 1.20, 1.14 (6H, s, 2CH3); 1.04, 0.93
(10H, m, 5CH2); 0.79 (12H, m, 3CH2, 2CH3).
1
427 (m), 415 (m). H NMR (d ppm, CDCl3): 9.69 (8H,
m, Ha); 8.51 (8H, m, Hb); 5.07 (2H, d, 2CH); 2.90 (6H,
q, 2OCH3); 1.52 (6H, q, 2CH3); 0.89 [18H, m, 2C(CH3)3];
0.54 (6H, q, 2CH3).
2.3.13. Synthesis of bis(1,1,1,5,5,5-hexafluoro-2,4-pentane-
dionato)zirconium(IV) phthalocyanine (XIII)
It was prepared from PcZrCl2 and 1,1,1,5,5,5-hexa-
fluoro-2,4-pentandione by the same procedure as (V).
Yield: 43%. Anal. Calc. for C42H18F12N8O4Zr: C, 49.56;
H, 1.78; N, 11.01; Zr, 8.96. Found: C, 49.20; H, 1.50; N,
10.50; Zr, 9.05%. (KBr, cmꢀ1): 1700 (sh), 1685 (s), 1662
(s), 1650 (s), 1612 (s), 1600 (sh), 1560 (w), 1510 (m), 1475
(m), 1425 (m), 1400 (m), 1335 (s), 1290 (s), 1260 (m),
1210 (s), 1165 (s), 1145 (m), 1120 (s), 1078 (s), 1065 (sh),
900 (m), 830 (m), 775 (m), 750 (m), 740 (s), 730 (sh), 430
2.3.10. Synthesis of bis(2,4-decanedionato)hafnium(IV)
phthalocyanine (X)
1
It was prepared from PcHfCl2 and 2,4-decandione by
the same procedure as (V). Yield: 47%. Anal. Calc. for
C52H50N8O4Hf: C, 60.67; H, 4.90; N, 10.88; Hf, 17.34.
Found: C, 60.50; H, 5.00; N, 10.45; Hf, 17.34%. IR
(KBr, cmꢀ1): 2930 (m), 2860 (m), 1605 (s), 1593 (s), 1578
(s), 1570 (s), 1530 (s), 1506 (s), 1465 (m), 1418 (m), 1400
(m), 1375 (m), 1362 (sh), 1330 (s), 1285 (s), 1160 (m),
1118 (s), 1080 (sh), 1070 (s), 1050 (m), 900 (m), 825 (m),
(m), 425 (sh). H NMR (d ppm, CDCl3): 9.25 (8H, m,
Ha); 8.11 (8H, m, Hb); 4.70 (2H, s, 2CH).
2.3.14. Synthesis of bis(1,1,1,5,5,5-hexafluoro-2,4-pentane-
dionato)hafnium(IV) phthalocyanine (XIV)
It was prepared from PcHfCl2 and 1,1,1,5,5,5-hexa-
fluoro-2,4-pentandione by the same procedure as (V).
Yield: 45%. Anal. Calc. for C42H18F12N8O4Hf: C, 45.65;
H, 1.64; N, 10.14; Hf, 16.15. Found: C, 45.40; H, 1.50;
N, 10.00; Hf, 16.25%. IR (KBr, cmꢀ1): 1680 (sh), 1663
(s), 1648 (s), 1610 (m), 1555 (w), 1509 (m), 1478 (m),
1420 (m), 1395 (w), 1380 (s), 1295 (s), 1257 (s), 1213 (s),
1160 (s), 1140 (s), 1120 (s), 1080 (s), 1070 (sh), 900 (m),
815 (m), 780 (m), 750 (m), 740 (s), 730 (s), 430 (m), 425
1
775 (m,d), 750 (s), 740 (s), 435 (m), 425 (sh). H NMR (d
ppm, CDCl3): 9.43 (8H, m, Ha); 8.14 (8H, m, Hb); 4.14
(2H, d, 2CH); 1.54; 1.27 (4H, m, 2CH2); 1.18; 1.12 (6H,
s, 2CH3); 1.04; 0.93 (10H, m, 5CH2); 0.79 (12H, m,
3CH2, 2CH3).
1
2.3.11. Synthesis of bis(2-methoxy-2,6,6-trimethyl-3,5-hep-
tanedionato)zirconium(IV) phthalocyanine (XI)
(sh). H NMR (d ppm, CDCl3): 9.17 (8H, m, Ha); 8.10
(8H, m, Hb); 4.60 (2H, s, 2CH).
It was prepared from PcZrCl2 and 2-methoxy-2,6,6-tri-
methyl-3,5-heptanedione by the same procedure as (V).
Yield: 51%. Anal. Calc. for C54H54N8O6Zr: C, 64.71; H,
5.43; N, 11.18; Zr, 9.10%. Found: C, 64.50; H, 5.50; N,
10.90; Zr, 9.25%. (KBr, cmꢀ1): 2950 (m), 1615 (sh), 1590
(s), 1570 (s), 1550 (sh), 1510 (s), 1470 (m), 1420 (m), 1409
(m), 1400 (sh), 1365 (m), 1335 (s), 1290 (s), 1235 (m),
1180 (m), 1168 (m), 1120 (s), 1080 (s), 960 (m), 938 (m),
900 (m), 780 (m), 770 (m), 750 (s), 740 (s), 430 (m), 425
(sh).1H NMR (d ppm, CDCl3): 9.65 (8H, m, Ha); 8.42
(8H, m, Hb); 5.01 (2H, d, 2CH); 2.83 (6H, q, 2OCH3);
1.40 (6H, q, 2CH3); 0.78 [18H, m, 2C(CH3)3]; 0.46 (6H,
q, 2CH3).
2.3.15. Synthesis of bis(1-phenyl-4,4,4-trifluoro-1,3-butane-
dionato)zirconium(IV) phthalocyanine (XV)
It was prepared from PcZrCl2 and 1-phenyl-4,4,4-tri-
fluoro-1,3-butandione by the same procedure as (V). Yield:
57%. Anal. Calc. for C52H28F6N8O4Zr: C, 60.40; H, 2.73;
N, 10.84; Zr, 8.82. Found: C, 60.05; H, 2.65; N, 10.35;
Zr, 8.55%. IR (KBr, cmꢀ1): 3050 (w), 1625 (sh), 1615 (s),
1600 (s), 1578 (s), 1570 (sh), 1543 (m), 1508 (s), 1492 (sh),
1470 (m), 1420 (m), 1335 (s), 1325 (s), 1298 (s), 1290 (sh),
1250 (s), 1200 (s), 1165 (m), 1145 (s), 1120 (s), 1100 (sh),
1075 (s), 1030 (m), 900 (m), 830 (m), 820 (m), 780 (s),
755 (s), 743 (s), 725 (sh), 705 (s), 680 (m), 450 (m), 440

2576
L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
(sh). 1H NMR (d ppm, CDCl3): 9.27 (8H, m, Ha); 8.21 (8H,
m, Hb); 7.56 (2H, q, 2C6H5); 7.25 (4H, q, 2C6H5); 6.96 (4H,
t, 2C6H5); 5.52 (2H, s, 2CH).
10 mmol of 3-chloro-2,4-pentanedione was added to the
solution. The mixture was heated under reflux for 10–
15 min. After completion of the reaction a small amount
of water was added to the solution which was cooled down
to start the crystallization. The formed precipitate was fil-
trated, washed with cool isopropyl alcohol and air-dried,
finally dried in vacuum at 60 ꢁC. Yield = 87%.
2.3.16. Synthesis of bis(1-phenyl-4,4,4-trifluoro-1,3-butane-
dionato)hafnium(IV) phthalocyanine (XVI)
It was prepared from PcHfCl2 and 1-phenyl-4,4,4-tri-
fluoro-1,3-butandione by the same procedure as (V). Yield:
61%. Anal. Calc. for C52H28F6N8O4Hf: C, 55.70; H, 2.52;
N 9.99; Hf, 15.92. Found: C, 55.20; H, 2.15; N, 10.15;
Hf, 15.85%. (KBr, cmꢀ1): 3060 (w), 1625 (m), 1610 (s),
1599 (s), 1565 (sh), 1542 (m), 1505 (m), 1495 (sh), 1470
(m), 1460 (sh), 1420 (m), 1335 (s), 1325 (s), 1300 (s), 1295
(sh), 1250 (s), 1200 (s), 1188 (sh) 1160 (m), 1148 (s), 1120
(s), 1100 (sh), 1080 (s), 1050 (m), 898 (m), 820 (m), 810
(m), 770 (s), 750 (s), 740 (s), 725 (m), 700 (s), 685 (sh),
2.3.20. Synthesis of bis(N1-(4-metoxyphenyl)-2-
(1-acetyl-2-oxopropylsulfanyl)acetamido) zirconium(IV)
phthalocyanine (XIX)
1.00 mmol of PcZrCl2 was suspended in 10 ml xylene
and then 2.20 mmol of N1-(4-metoxyphenyl)-2-(1-acetyl-
2-oxopropylsulfanyl)acetamide was added to the suspen-
sion. The reaction mixture was heated under reflux for
4 h after which the hot mixture was filtrated. The solvent
volume was reduced by 50% using vacuum evaporation
and the final product was precipitated by hexane. Blue-
green crystals were formed slowly while the solution was
cooling down. The product was filtered, abundantly
washed by hexane, air-dried and eventually dried under
vacuum at 100 ꢁC. Yield: 67%. Anal. Calc. for
C60H48N10O8S2Zr: C, 60.44; H, 4.06; N, 11.75; Zr, 7.65.
Found: C, 60.15; H, 3.85; N, 11.25; Zr, 7.50%. IR (KBr,
cmꢀ1): 3050 (w), 1615 (m), 1580 (s), 1565 (sh), 1525 (s),
1505 (s), 1465 (m), 1420 (m), 1390 (m), 1370 (m), 1360
(m), 1330 (s), 1285 (s), 1210 (w), 1185 (w), 1160 (s), 1115
(s), 1075 (s), 1030 (m), 1000 (m), 980 (sh), 950 (w), 935
(w), 895 (s), 870 (m), 810 (m), 780 (s), 750 (s), 740 (s),
725 (w), 670 (w), 640 (m), 580 (m), 530 (w), 510 (m), 495
(w), 460 (m), 280 (m). 1H NMR (d ppm, CDCl3): 9.47
(4H, q, Ha); 9.33 (4H, q, Ha); 8.20 (4H, q, Hb); 8.10 (4H,
q, Hb); 7.27 (4H, d., 2C6H4); 7.18 (2H, s, 2NH); 6.83
(4H, d., 2C6H4); 3.78 (6H, s, 2OCH3); 2.19 (4H, s,
2CH2); 1.51 (12H, s, 4CH3).
1
440 (m), 430 (sh). H NMR (d ppm, CDCl3): 9.37 (8H,
m, Ha); 8.02 (8H, m, Hb); 7.39 (2H, q, 2C6H5); 7.08 (4H,
q, 2C6H5); 6.65 (4H, t, 2C6H5); 5.06 (2H, s, 2CH).
2.3.17. Synthesis of bis(1-phenyl-1,3-butanedionato)zirco-
nium(IV) phthalocyanine (XVII)
It was prepared from PcZrCl2 and 1-phenyl-1,3-but-
andione by the same procedure as (V). Yield: 53%. Anal.
Calc. for C52H34N8O4Zr: C, 67.44; H, 3.70; N, 12.10; Zr,
9.85. Found: C, 67.50; H, 3.50; N, 11.85; Zr, 10.00%. IR
(KBr, cmꢀ1): 3060 (w), 1605 (sh), 1592 (s), 1552 (s), 1530
(sh), 1522 (s), 1510 (sh), 1490 (m), 1465 (m), 1420 (m),
1375 (m), 1365 (sh), 1335 (s), 1310 (m), 1285 (m), 1160
(m), 1115 (s), 1075 (s), 1030 (m), 895 (m), 840 (m), 820
(m), 770 (s), 750 (s), 735 (s), 710 (s), 685 (m), 430 (m),
1
425 (sh). H NMR (d ppm, CDCl3): 9.66–9.02 (8H, m,
Ha); 8.28–7.96 (8H, m, Hb); 7.41 (2H, q, –C6H5); 7.16
(4H, q, –C6H5); 6.87 (4H, t, –C6H5); 4.97 (2H, s, 2CH);
1.40 (6H, s, –CH3).
2.3.18. Synthesis of bis(1-phenyl-1,3-butanedionato)
hafnium(IV) phthalocyanine (XVIII)
2.3.21. Synthesis of bis(N1-(4-metoxyphenyl)-2-(1-acetyl-
2-oxopropylsulfanyl)acetamido) hafnium(IV) phthalocya-
nine (XX)
It was prepared from PcHfCl2 and 1-phenyl-1,3-but-
andione by the same procedure as (V). Yield: 56%. Anal.
Calc. for C52H34N8O4Hf: C, 61.63; H, 3.38; N, 11.06; Hf,
17.61. Found: C, 61.50; H, 3.25; N, 10.85; Hf, 17.50%.
IR (KBr, cmꢀ1): 3070 (w), 1600 (sh), 1592 (s), 1555 (s),
1535 (sh), 1525 (s), 1510 (sh), 1490 (m), 1470 (m), 1420
(m), 1380 (m), 1365 (sh), 1335 (s), 1312 (m), 1286 (m),
1160 (m), 1117 (s), 1077 (s), 1030 (m); 900 (s), 854 (m),
820 (m), 770 (s), 750 (s), 737 (s), 710 (s), 685 (m), 435
It was prepared from PcHfCl2 and N1-(4-metoxyphe-
nyl)-2-(1-acetyl-2-oxopropylsulfanyl)acetamide by the
same procedure as XIX. Yield: 66%. Anal. Calc. for
C60H48N10O8S2Hf: C, 56.31; H, 3.78; N, 10.95; Hf, 13.95.
Found: C, 56.35; H, 3.75; N, 10.25; Hf, 13.50%. IR
(KBr, cmꢀ1): 3060 (w), 1610 (m), 1580 (s), 1570 (sh),
1525 (s), 1505 (s), 1465 (m), 1420 (m), 1390 (m), 1370
(m), 1360 (m), 1330 (s), 1285 (s), 1210 (w), 1185 (w), 1160
(s), 1115 (s), 1075 (s), 1030 (m), 1000 (m), 980 (sh), 950
(w), 935 (w), 895 (s), 870 (m), 810 (m), 780 (s), 750 (s),
740 (s), 725 (w), 670 (w), 640 (m), 580 (m), 530 (w), 500
1
(m), 425 (sh). H NMR (d ppm, CDCl3): 9.61–9.04 (8H,
m, Ha); 8.28–7.99 (8H, m, Hb); 7.40 (2H, q, C6H5); 7.13
(4H, q, –C6H5); 6.85 (4H, t, –C6H5); 4.92 (2H, s, 2CH);
1.36 (6H, s, –CH3).
1
(m), 490 (w), 440 (m), 280 (m). H NMR (d ppm, CDCl3):
9.42 (4H, q, Ha); 9.28 (4H, q, Ha); 8.25 (4H, q, Hb); 8.07
(4H, q, Hb); 7.29 (4H, d., 2C6H4); 7.16 (2H, s, 2NH);
6.81 (4H, d., 2C6H4); 3.77 (6H, s, 2OCH3); 2.15 (4H, s,
2CH2); 1.45 (12H, s, 4CH3).
2.3.19. Synthesis of N1-(4-metoxyphenyl)-2-(1-acetyl-2-
oxopropylsulfanyl)acetamide
10 mmol of N1-(4-metoxyphenyl)-2-sulfanylacetamide
was dissolved in 5 ml of 2N KOH in isopropanol. Then

L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
2577
1
2.3.22. Synthesis of bis(4-benzoyl-3-methyl-1-phenyl-2-
pyrazolin-5-onato)zirconium(IV) phthalocyanine (XXI)
It was prepared from PcZrCl2 and 4-benzoyl-3-methyl-
1-phenyl-2-pyrazolin-5-one by the same procedure as
XIX. Yield: 71%. Anal. Calc. for C66H42N12O4Zr: C,
68.44; H, 3.65; N, 14.51; Zr, 7.87. Found: C, 68.05; H,
3.15; N, 14.10; Zr, 7.50%. IR (KBr, cmꢀ1): 3070 (m),
2930 (w), 2870 (w), 2650 (w), 2610 (w), 2560 (m), 1620
(s), 1605 (s), 1570 (s), 1530 (m), 1505 (s), 1485 (s), 1470
(m), 1445 (m), 1425 (m), 1390 (m), 1365 (w), 1336 (s),
1290 (s), 1255 (w), 1215 (w), 1166 (s), 1120 (s), 1080 (s),
1030 (m), 1005 (w), 960 (m), 900 (s), 880 (w), 850 (m),
830 (m), 800 (w), 785 (w), 760 (m), 755 (s), 740 (s), 705
(m), 695 (m), 670 (w), 630 (m), 560 (w), 510 (m), 455 (w),
435 (w), 355 (w), 300 (m). 1H NMR (d ppm, CDCl3):
9.45 (2H, d, Ha); 9.25 (4H, d, Ha); 8.81 (2H, d, Ha); 8.22
(2H, t, Hb); 8.04 (6H, m, Hb); 7.44 (2H, q, 4C6H5); 7.35
(4H, q, 4C6H5); 7.18 (4H, t, 4C6H5); 7.05 (6H, q, 4C6H5);
6.88 (4H, q, 4C6H5); 1.34 (3H, s, CH3); 1.25 (3H, s, CH3).
The results obtained from IR, H NMR spectroscopy
and elemental analysis suggest that substitution of two Cl
atoms for two b-dicarbonyl ligands takes place as the result
of the reaction between PcZrCl2 or PcHfCl2 and free b-
dicarbonyl compounds. The isolated complexes with addi-
tional axial ligands are soluble in most organic solvents
(DMSO, toluene, chloroform and other). However, deter-
mination of the complexes structure by X-ray methods is
difficult because of obstacle to grow monocrystal of opti-
mal size. Instead of X-ray diffraction the methods of two
dimension NMR spectroscopy (COSY, NOESY, ROESY)
have been used for studying the structure of the synthesized
out-planed substitution phthalocyanine complexes of zirco-
nium(IV) and hafnium(IV).
1
2D H NMR COSY and NOESY spectra of bis(2,4-
pentanedionato)hafnium(IV) chlorinephthalocyanine (V)
shown in Fig. 1 reveal that the interaction protons (out
of diagonal signals) are related to the compounds of dif-
ferent structure. Analogous effect can be observed for the
zirconium complex (VI). It allows asserting that analyzed
complexes consist of the mixture of structural monochlo-
rinated phthalocyanine isomers. For all the investigated
mixed ligand complexes 2D 1H NMR spectra, COSY
2.3.23. Synthesis of bis(4-benzoyl-3-methyl-1-phenyl-2-
pyrazolin-5-onato)hafnium(IV) phthalocyanine (XXII)
It was prepared from PcHfCl2 and 4-benzoyl-3-methyl-
1-phenyl-2-pyrazolin-5-one by the same procedure as
XIX. Yield: 69%. Anal. Calc. for C66H42N12O4Hf: C,
63.64; H, 3.40; N, 13.49; Hf, 14.33. Found: C, 63.10; H,
3.00; N, 13.05; Hf, 14.50%. IR (KBr, cmꢀ1): 3070 (m),
2930 (w), 2870 (w), 2650 (w), 2610 (w), 2560 (m), 1625
(s), 1615 (s), 1610 (s), 1575 (s), 1530 (m), 1505 (s), 1485
(s), 1470 (m), 1445 (m), 1425 (m), 1390 (m), 1365 (w),
1336 (s), 1290 (s), 1255 (w), 1210 (w), 1166 (s), 1120 (s),
1080 (s), 1030 (m), 1005 (w), 960 (m), 900 (s), 880 (w),
850 (m), 830 (m), 800 (w), 785 (w), 760 (m), 755 (s), 740
(s), 705 (m), 695 (m), 670 (w), 630 (m), 560 (w), 510 (m),
455 (w), 435 (w), 355 (w), 275 (m). 1H NMR (d ppm,
CDCl3): 9.44 (2H, d, Ha); 9.25 (4H, d, Ha); 8.81 (2H, d,
Ha); 8.22 (2H, t, Hb); 8.04 (6H, m, Hb); 7.44 (2H, q,
4C6H5); 7.28 (4H, q, 4C6H5); 7.16 (4H, t, 4C6H5); 7.03
(6H, q, 4C6H5); 6.86 (4H, q, 4C6H5); 1.34 (3H, s, CH3);
1.23 (3H, s, CH3).
exhibit only correlation between H–bH protons in phtha-
locyanine N8 ring and protons from out-plane ligands.
The interactions between ring and ligands protons have
a
1
not been found. At the same time in the 2D H NMR
spectra NOESY for complex XVII shown in Fig. 2,
besides diagonal crossing signals also can be observed
the signals which arise from the space interaction between
phthalocyanine ring protons and protons of the out
planed ligands. For example, it can be seen for methyl
and aH protons or phenyl and bH. It proves that the
angle between the b-dicarbonilate ligand plane and the
phthalocyanine ring plane is very sharp and the coordina-
tion junction has cis-configuration. The analogous data
have been obtained for the other mixed ligands b-(dicar-
bonilato)zirconium and hafnium phthalocyanines. The
2D NOESY experiment for complexes XIX (Fig. 3) and
XX nicely illustrates the NOE cross peaks between bH
(Pc) and CH2, NH, p-C6H4 (Ar) protons of the out
a
3. Results and discussion
planed ligands; H (Pc) and CH3. To determine the struc-
ture of complexes XXI and XXII, NOESY and ROESY
Two chlorine atoms bound to the central metal atom of
dichloro(phthalocyaninato) zirconium(IV) or hafnium(IV)
are highly mobile and can be easily exchanged for various
organic ligands [23–26]. This ability makes possible synthe-
sis the ‘‘out-of-plane’’ directly to the metal substituted
phthalocyanine complexes with the tailor-made properties.
Phthalocyanine ring is the p-conjugated macrocycle that
has interesting spectral, electrochemical and optical prop-
erties. Introduction of two b-dicarbonyl fragments leads
to the expansion of p-conjugated system and due to one’s
turn changes spectral luminescent behaviour. It must be
emphasised that we mean not only p-conjugated Pc ring
but the whole system where metal play role of connector
between Pc ring and two b-dicarbonyl ligands.
correlations between protons of phenyl groups of 4-ben-
a
zoyl-3-methyl-1-phenyl-2-pyrazolin-5-one and H–bH pro-
tons of Pc macrocycle have been analyzed (Figs. 4a and
b). Besides diagonal crossing signals also ROE correla-
tions for aH (Pc)–CH3 and bH (Pc)–H (Ph) have been
observed. In addition, two signals coming from the
methyl groups of DMF could be observed. Inasmuch sig-
nals of DMF methyl groups are present on all the spectra
shown in Figs. 2–4 and also interaction between these
DMF protons and protons from both phthalocyanine
ring and out-planed ligands are present, we can conclude
that molecule of DMF is solvated in a cavity between
the ‘‘out of plane’’ dicarbonilato ligand and the N8
macrocycle.

2578
L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
Fig. 2. 2D NMR spectra of complex XVII (CDCl3): NOESY (a, b).
Fig. 1. 2D NMR spectra of complex VI (CDCl3): COSY (a) and NOESY
(b).
quasi aromatic cyclic system. Delocalization of p electrons
in the conjugated system and presence of free d-electron
orbitals of the central metal atom have important influence
on the HOMO–LUMO transitions and, as a result, the
bathochromic shift of the Q-absorption band is observed
in the spectra. For these reasons, metal-containing and
out of plane substituted phthalocyanines which absorb
intensively in the visible light region, could be used as
photoconverters. Photoconverters have to absorb light
energy suitable for the energy gap of the semiconductors.
The shape of the UV–Vis spectra does not change dramat-
ically in various solvents and only a small shift of the Q-
band position is observed. At the same time, insignificant
change of the molar absorption coefficient value takes
3.1. Luminescence properties
UV–Vis absorption spectra provide information about
the possibility of the absorption transition between the
ground and excited states of dye molecule. Two absorption
bands, the intense Q band at 680–695 nm and less intensive
Soret band at 320–360 nm are present in the spectra of
bis(b-dicarbonilato)zirconium(IV) and hafnium(IV) phtha-
locyanine complexes (Table 1). Examples of the UV–Vis
absorption spectra for compounds VII, XIX, and XXI in
DMSO solutions are shown in Fig. 5. Addition of two b-
dicarbonyl ligands leads to the expansion of p-conjugated
system as b-dicarbonyl forms together with metal atom

L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
2579
Fig. 3. 2D NMR spectra NOESY of complex XIX (CDCl3).
place (Table 1, Fig. 6). For all the investigated complexes,
except VII and IX, the increasing of the molar absorption
coefficient occurs in the series DMSO–THF–toluene. This
sequence is in good agreement with Reichardt’s solvents
polarity parameters [27]. The lowest value of the molar
absorption coefficient is observed in DMSO (polarity
parameter 0.444), higher for THF (0.207) and the highest
for toluene (0.099). Process of phthalocyanine dimerization
is easier in the more polar solvents.
The fluorescent properties of the investigated complexes
III, VII, IX, XI, XIII, XV, XIX and XXI were studied in the
same solvents: toluene, DMSO and THF. All studied zirco-
nium phthalocyanine complexes show weaker fluorescence
than zinc phthalocyanine (Table 1). The complex XV gives
fluorescent activity only in DMSO solution (Fig. 7). At the
same conditions PcHfCl2 and other synthesized hafnium
phthalocyanine complexes do not exhibit any fluorescence.
This phenomenon is known and explained by the effect of
the ‘‘heavy’’ atom.
Fig. 4. 2D NMR spectra of complex XXI (CDCl3): NOESY (a) and
ROESY (b).
as a reference standard. The natural lifetimes of the stud-
ied phthalocyanine complexes were evaluated from
absorption and fluorescence spectra by the known meth-
od described in references [11,28], using the following
equation:
The fluorescence quantum yields of dyes were deter-
mined by the comparative method [11,28] on the ground
of the UV–Vis and fluorescence spectra, using the follow-
ing equation:
R
Z
F ðkÞ dk
1
eðkÞ
k2
¼ 2:288 ꢂ 10ꢀ9 ꢁ n2 ꢁ
dk ꢁ
;
ð2Þ
R
n2 ꢁ S ꢁ AR
s
k
F ꢁ ðkÞdk
U ¼ UR ꢁ
;
ð1Þ
2
ðnRÞ ꢁ SR ꢁ A
where n is refractive index, and integrals of F(k) and e(k)
are the areas under the fluorescence and absorption spec-
tra, respectively.
where UR is the fluorescence quantum yield of the refer-
ence, S and SR are the areas under the fluorescence
curves of the sample and reference, respectively; A and
AR are the absorption intensities of the sample and ref-
erence, respectively; n and nR are refractive indexes for
the sample and reference, respectively. Zinc phthalocya-
nine (PcZn) in DMSO solution (UR = 0.20) [29] was used
The fluorescence quantum yields were determined by
formula (1) and natural lifetimes were calculated on the
basis of the absorption and fluorescence data (Eq. (2)).
For the investigated complexes containing the alkyl frag-
ments in the out of plane ligands, the highest values of

2580
L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
Table 1
Spectral and photophysical measurements
Complex
PcZn
Solvent
Abs. kmax (nm)
e · 105
Fluoresc. kmax (nm)
n20
UF
Dk (nm)
s (ns)
Toluene
DMSO
THF
670
673
666
3.4209
1.5900
2.3305
676
686
678
1.496
1.478
1.408
0.07
0.2
0.23
6
13
12
2.41
6.76
5.36
III
DMSO
688
1.1646
697
1.479
0.006
11
14.17
VII
Toluene
DMSO
THF
688
684
684
0.8276
1.3140
1.6225
703
702
697
1.497
1.479
1.407
0.024
0.073
0.032
15
18
13
1.66
6.33
5.34
IX
Toluene
DMSO
THF
688
686
682
1.9971
1.489
2.1950
701
703
696
1.498
1.478
1.407
0.042
0.072
0.069
13
17
12
1.66
5.42
4.09
XI
Toluene
DMSO
THF
682
685
683
7.246
1.610
2.356
695
697
690
1.496
1.480
1.407
0.004
0.069
0.029
13
12
7
1.27
5.72
4.59
XIII
XV
XIX
XXI
Toluene
DMSO
THF
686
682
680
2.871
0.8995
1.1300
702
700
692
1.497
1.480
1.408
0.063
0.075
0.117
16
18
12
2.58
8.87
7.78
Toluene
DMSO
THF
686
686
686
4.942
1.2360
1.7725
1.496
1.479
1.408
693
0.066
6.20
Toluene
DMSO
THF
686
692
688
3.083
1.1005
1.7750
703
702
691
1.497
1.478
1.407
0.029
0.067
0.038
17
10
3
2.55
6.99
4.94
Toluene
DMSO
THF
691
694
690
4.323
1.4995
2.3065
708
709
701
1.496
1.478
1.406
0.073
0.063
0.061
17
15
11
1.99
5.79
4.12
1.0
0.8
0.6
0.4
0.2
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0.0
300
400
500
600
700
800
900
300
400
500
600
700
800
λ [nm]
λ [nm]
Fig. 5. Electronic absorption spectra of Zr(IV) axially substituted
phthalocyanines VII (dash-dotted), XIX (dashed), XXI (solid line)
2 · 10ꢀ6 mol/dm3 solutions in DMSO.
Fig. 6. Electronic absorption spectra of Zr(IV) axially substituted
phthalocyanine (XXI) 2 · 10ꢀ6 mol/dm3 solutions in DMSO (solid),
THF (dotted) and toluene (dashed line).
that makes molecule more rigid and in consequence leads
to increasing of fluorescence quantum yield. This regular-
ity does not take place for complexes XIII and XXI.
Complex XIII in THF has the highest values of fluores-
cence quantum yield (UF = 11.7%). It can be explained
by the structure of complex XIII, which contains
1,1,1,5,5,5-hexafluoro-2,4-pentanedione ligand. In other
words, the introduction of electronegative fluorine atoms
fluorescence quantum yields are observed in DMSO. For
these complexes, some increasing of fluorescence quantum
yields is observed in the sequence: toluene–THF–DMSO,
analogous with the same effect in the absorption spectra.
It can be explained by the increasing viscosity of the sol-
vents. Increasing of solvent viscosity leads to braking of
the free rotation alkyl fragments in out of plane ligands

L.A. Tomachynski et al. / Inorganica Chimica Acta 361 (2008) 2569–2581
2581
30000
25000
20000
15000
10000
5000
0
no tendency to the aggregation; however, absorbance
slightly decreases with higher solvent polarity. Fluores-
cence quantum yields and natural life times of zirconium
phthalocyanine complexes have been calculated in toluene,
DMSO and THF. Correlation between the structure of
phthalocyanine mixed ligand complexes and the properties
of the solvents from one side and spectral luminescent
properties from the other was been found.
References
[1] N.B. McKeown, Phthalocyanine Materials – Synthesis, Structure,
and Function, Cambridge University Press, New York, 1998.
[2] J. Limson, T. Nyokong, Electroanalysis 9 (1997) 255.
[3] K. Morishige, S. Tomoyasu, G. Iwano, Langmuir 13 (1997) 5184.
[4] M.H. Zahir, Y. Kagaya, H. Isago, T. Furubayashi, Inorg. Chim. Acta
357 (2004) 2755.
[5] J.W. Owens, R. Smith, R. Robinson, M. Robins, Inorg. Chim. Acta
279 (1998) 226.
[6] H. Ali, J.E. van Lier, Chem. Rev. 99 (1999) 2379.
[7] R. Bonnet, Chemical Aspects of Photodynamic Therapy, Gordon and
Breach Science, Amsterdam, 2000.
580
600
620
640
660
680
λ [nm]
700
720
740
760
780
Fig. 7. Excitation (kdet = 696 nm) (solid) and fluorescence (kexc = 686 nm)
(dashed line) spectra of Zr(IV) axially substituted phthalocyanine (XV)
2 · 10ꢀ6 mol/dm3 in DMSO solution.
leads to shift of electronic density in ligand and, respec-
tively, via metal atom in Pc macrocycle, what have signif-
icant influence on the HOMO–LUMO transitions. Two p-
conjugated pyrazolone ligands are introduced in complex
XXI. In result this compound must be considered as rigid
p-conjugated system.
The natural lifetimes of studied phthalocyanines are in
the range of nanoseconds. It means that the energy transfer
should be reachable for about 10ꢀ9 s before the excited
molecule turns spontaneously to its ground state. The sub-
stitution of two out planed Cl atoms for two b-dicarbonyl
fragments leads to increasing of fluorescence quantum yield
and decreasing of the natural lifetimes (Table 1). The max-
imum values of the natural lifetimes for studied complexes
are in DMSO. The Stokes shifts between the absorption Q-
band and the fluorescence maximum are very small (3–
18 nm) for all investigated PcZrL2.
[8] E.I. Yslas, V. Rivarola, E.N. Durantini, Bioorg. Med. Chem. 13
(2005) 39.
[9] C. Rager, G. Schmid, M. Hanack, Chem. Eur. J. 5 (1999) 280.
[10] M.J. Cook, Chem. Rec. 2 (2002) 225.
[11] D. Wrobel, A. Boguta, J. Photochem. Photobiol. A: Chem. 150 (2002)
67.
[12] W.-F. Law, R.C.W. Liu, J. Jiang, D.K.P. Ng, Inorg. Chim. Acta 256
(1997) 147.
[13] J.S. Shrik, R.G. S Pong, S.R. Flom, H. Heckmann, M. Hanack, J.
Phys. Chem. A 104 (2000) 1438.
[14] M. Barthel, M. Hanack, J. Porphyrins Phthalocyanines 4 (2007)
635.
[15] W. Sun, G. Wang, Y. Li, M.J.F. Calvete, D. Dini, M. Hanack, J.
Phys. Chem. A 111 (2007) 3263.
[16] L.A. Tomachynski, V.Ya. Chernii, S.V. Volkov, J. Porphyrins
Phthalocyanines 10 (2001) 731.
[17] L.A. Tomachynski, Yu.Yu. Kolotilova, V.Ya. Chernii, S.V. Volkov,
Zh. Theor. Exp. Chimii 39 (2003) 96.
[18] M.P. Donzello, C. Ercolani, P.J. Lukes, Inorg. Chim. Acta 256 (1997)
171.
[19] Z.N. Chen, R. Appelt, H. Vahrenkamp, Inorg. Chim. Acta 309 (2000)
65.
[20] J. Janczak, Y.M. Idemori, Inorg. Chim. Acta 325 (2001) 85.
[21] D. Dini, M. Hanack, H.-J. Egelhaaf, J.C. Sancho-Garcia, J. Cornil, J.
Phys. Chem. B 109 (2005) 5432.
[22] L.A. Tomachynski, V.Ya. Chernii, S.V. Volkov, J. Inorg. Chem.
(Rus.) 47 (2002) 208.
[23] L.A. Tomachynski, V.Ya. Chernii, S.V. Volkov, J. Porphyrins
Phthalocyanines 10 (2001) 731.
[24] L.A. Tomachynski, V. Ya Chernii, S.V. Volkov, J. Porphyrins
Phthalocyanines 6 (2002) 90.
[25] L.A. Tomachynski, V.Ya. Chernii, H.N. Gorbenko, V.V. Filonenko,
S.V. Volkov, Chem. Biodiv. 1 (2004) 862.
[26] I.N. Tretyakova, V.Ya. Chernii, L.A. Tomachynski, S.V. Volkov, Zh.
Theor. Exp. Chimii 42 (2006) 142.
[27] Ch. Reichardt, Solvents and Solvent Effects in Organic Chemistry,
VCH, New York, 1988.
4. Conclusions
The series of zirconium(IV) and hafnium(IV) phthalocy-
anines with various b-dicarbonyl ligands has been synthe-
sized. The structure of the obtained bis(b-dicarbonilato)
zirconium(IV) and hafnium(IV) phthalocyanines was stud-
ied by two dimension 1H NMR spectroscopy (COSY,
NOESY, ROESY). The interaction between phthalocya-
nine and out of plane ligand protons allows determining
the structure of macromolecule by NOESY and ROESY
techniques. It was concluded that additionally the molecule
of DMF is solvated in a cavity between the ‘‘out of plane’’
dicarbonilato ligand and the N8 macrocycle.
Absorption and fluorescence spectroscopic properties
were studied in three solvents with different polarity. In
the concentration range of 10ꢀ6 M/dm3, there is rather
[28] D. Wrobel, C.R. Chimie 6 (2003) 417.
[29] A. Ogunsipe, D. Maree, T. Nyokong, J. Mol. Struct. 650 (2003)
131.