Synthesis and characterization of novel tetrapyrazinoporphyrazine derivatives containing morpholine and tert-butyl group

Article abstract of DOI:10.1080/15421400903054121

Tetrapyrazinoporphyrazine magnesium complexes were synthesized from 2,3-dicyano-5-(4-alkylphenyl)-6-(4-morpholinophenyl)pyrazine derivatives using freshly prepared solutions of magnesium butoxide in n-butanol. The corresponding metal-free derivatives were

Full text of DOI:10.1080/15421400903054121

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Synthesis and
Characterization of Novel
Tetrapyrazinoporphyrazine
Derivatives Containing
Morpholine and tert-Butyl
Group
Song Hak Kim a , Do Kyung Lee a , Chun Keun Jang a ,
Seung Hwan Byun a & Jae-Yun Jaung a
a Department of Fiber and Polymer Engineering ,
Hanyang University , Seongdong-gu, Seoul, Republic
of Korea
Published online: 05 Oct 2009.
To cite this article: Song Hak Kim , Do Kyung Lee , Chun Keun Jang , Seung
Hwan Byun & Jae-Yun Jaung (2009) Synthesis and Characterization of Novel
Tetrapyrazinoporphyrazine Derivatives Containing Morpholine and tert-Butyl
Group, Molecular Crystals and Liquid Crystals, 509:1, 96/[838]-107/[849], DOI:
10.1080/15421400903054121
To link to this article: http://dx.doi.org/10.1080/15421400903054121
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Mol. Cryst. Liq. Cryst., Vol. 509, pp. 96=[838]–107=[849], 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400903054121
Synthesis and Characterization of Novel
Tetrapyrazinoporphyrazine Derivatives Containing
Morpholine and tert-Butyl Group
Song Hak Kim, Do Kyung Lee, Chun Keun Jang,
Seung Hwan Byun, and Jae-Yun Jaung
Department of Fiber and Polymer Engineering, Hanyang University,
Seongdong-gu, Seoul, Republic of Korea
Tetrapyrazinoporphyrazine magnesium complexes were synthesized from
2,3-dicyano-5-(4-alkylphenyl)-6-(4-morpholinophenyl)pyrazine derivatives using
freshly prepared solutions of magnesium butoxide in n-butanol. The correspond-
ing metal-free derivatives were obtained by treatment with p-toluenesulfonic
acid. Copper complexes were successfully synthesized using excess cuprous
chloride and DBU (1,8-diazabicyclo[5,4,0]-7-undecene) as a catalyst in o-dichlor-
obenzene under reflux. The tetrapyrazinoporphyrazines were characterized by
elemental analysis, UV-visible spectra, IR, MALDI-TOF Ms and 1H-NMR
spectra.
Keywords: 2,3-dicyanopyrazine; aggregation; bulky group; phthalocyanines; spectral
properties
INTRODUCTION
Unsubstituted metallophthalocyanines have intense colors but are
generally insoluble in both organic solvents and water, thereby limit-
ing their use to just a few fields. It is well known that the insolubility
This study was supported by a grant from the Fundamental R&D Program
(M200701004) for Core Technology of Materials funded by the Ministry of Commerce,
Industry and Energy, and a grant No. R01-2006-000-10489-0 from the Basic Research
Program of the Korea Science and Engineering Foundation and BK21 project in South
of Korea.
Address correspondence to Jae-Yun Jaung, Department of Fiber and Polymer
Engineering, Hanyang University, 17, Haengdang-dong, Seongdong-gu, Seoul,
133-791, Republic of Korea. E-mail: jjy1004@hanyang.ac.kr
96=[838]

Characterization of Novel Tetrapyrazinoporphyrazine Derivatives 97/[839]
of such phthalocyanine derivatives results from their molecular
stacking, which gives rise to strong intermolecular interactions
between the macrocycles in the phthalocyanine molecules. When
substituents are placed on the phthalocyanines ring, not only does
the solubility of the compounds increase, but supramolecular organi-
zation can be achieved as well, with steric hindrance of the peripheral
substituents reducing intermolecular p-p interactions. This effect
minimizes the formation of aggregates, improving solubility. In the
case of phthalocyanine macrocycles substituted with long alkyl chains,
segregation between the rigid aromatic moieties and the flexible
alkyl chains generally occurs, thereby resulting in the formation of
columnar mesophases [1].
Aggregation is usually depicted as a coplanar association of rings
progressing from monomer to dimer and higher order complexes.
Tetrapyrazinoporphyrazine macrocycles tend towards higher aggrega-
tion compared to phthalocyanine molecules. A lot of aggregation
inhibiting substituents have been developed as it is one of the most
undesirable properties which decreases solubility, causes problems
during purification, and shortens triplet state lifetimes crucial for
the effects of tetrapyrazinoporphyrazines in photodynamic therapy
[2]. These problems are usually solved through introduction of optimal
substituents onto the periphery of the tetrapyrazinoporphyrazine core
that suppress the aggregation.
2,3-Dicyanopyrazines for tetramerization (tetrapyrazinoporphyra-
zines) are usually built up through condensation of a-diketones and
diaminomaleonitrile, enabling peripheral substitutions typically not
available for phthalocyanines. Due to their interesting physical and
chemical properties, tetrapyrazinoporphyrazines have been investi-
gated in several applications [3]. Although they suffer from hypsochro-
mic shifts (blue shift) compared to corresponding phthalocyanines,
several types of peripheral substituents can induce important batho-
chromic shifts (red shift).
We have studied the syntheses of functional dye materials based on
2,3-dicyanopyrazine chromophores, and correlated their physical
properties with structure [4]. In this paper, we synthesized novel,
push-pull type pyrazine derivatives, bearing a morpholinophenyl
substituent as an electron donor group at the 6-position, and cyano-
substituents as electron acceptors at the 2- and 3-positions of
pyrazine. We also designed and synthesized metal and metal-free tet-
rapyrazinoporphyrazines derived from 2,3-dicyano-5-(4-alkylphenyl)-
6-(4-morpholinophenyl)pyrazine derivatives. Their aggregation
behaviors, depending on solvent polarity, were correlated with their
chemical structures.

98/[840]
S. H. Kim et al.
EXPERIMENTAL
Compounds were identified and their properties were measured using
the following techniques. Flash chromatography was performed with
Merch-EM type 60 (230–400 mesh) silica gel (flash). Melting points
were obtained with a capillary melting point apparatus and are uncor-
rected. 1H-NMR spectra were recorded on a VARIAN UnityInova
300 MHz FT-NMR spectrophotometer. UV-Vis spectra were measured
using a SCINCO S-4100 spectrophotometer. MALDI-TOF-Ms (matrix-
assisted laser desorption ionization time-of-flight mass) spectra were
obtained on a Waters Limited MALDI-TOF spectrometer with dithra-
nol as a matrix. Infrared spectra were taken on a MAGNA-IR 760
spectrometer using KBr pellets. Elemental analyses were performed
with CE Instruments-EA 1110 Automatic Elemental Analyzer. All
chemical were used of reagent grade without further purification
unless otherwise specified.
1. 1-(4-Morpolinophenyl)-2-(4-tert-
butylphenyl)ethan-1,2-Dione (1)
A
mixture of 1-(4-bromophenyl)-2-(4-tert-butylphenyl)ethan-1,2-
dione (1.72 g, 5 mmol), morpholine (0.65 g, 7.5 mmol), K2CO3 (1.38 g,
10 mmol), CuI (0.09 g, 0.5 mmol) and L-proline (0.11 g, 1 mmol) in
5 ml of DMSO was heated at 90ꢀC for 21 hr. The cooled mixture was
partitioned between water and ethyl acetate. The organic layer was
separated, and the aqueous layer was extracted with ethyl acetate.
The combined organic layers were washed with brine, dried over
Na2SO4, and concentrated in vacuo. The crude product was purified
by column chromatography over silica gel with ethyl acetate:hexane
(1:3) as eluent. 1 (yellow solid, 56%); m.p.: 94–96ꢀC; IR (KBr pellet):
v(cmꢁ1) 1677 (C¼O); H-NMR (300 MHz, CDCl3) d: 1.36 (s, –C(CH3)3,
9 protons), 3.34–3.37 (t, CH2, J ¼ 5.1 Hz, 4 protons), 3.81–3.86 (t,
CH2, J ¼ 4.8 Hz, 4 protons), 6.86 (d, Ar-H, J ¼ 9.3 Hz, 2 protons), 7.50
(d, Ar-H, J ¼ 8.7 Hz, 2 protons), 7.87 (d, Ar-H, J ¼ 9.3 Hz, 2 protons),
7.91 (d, Ar-H, J ¼ 6.9 Hz, 2 protons).
Elemental Anal. Calcd. For C22H25NO3: C, 75.19; H, 7.17; N, 3.99;
O, 13.66. Found: C, 75.16; H, 7.19; N, 3.90.
2. 1-(4-Tert-butylphenyl)-6-(4-morpholinophenyl)pyrazine-
2,3-dicarbonitrile (2)
A solution of diketone (1) (1.0 g, 2.845 mmol), 2,3-diaminomaleonitrile
(0.34 g, 3.186 mmol) and a small amount of p-toluenesulfonic acid as

Characterization of Novel Tetrapyrazinoporphyrazine Derivatives 99/[841]
catalyst in methanol (10 ml) was refluxed for 2 hr. After the reaction
was complete, the mixture was cooled at room temperature. The preci-
pitate was filtered off and washed with methanol. The crude product
was purified by column chromatography over silica gel with ethyl acet-
ate:hexane (1:3) as eluent. 2 (yellow solid, 73%); m.p.: 183–186ꢀC; IR
1
(KBr pellet): v(cmꢁ1) 2232 (CN); H-NMR (300 MHz, CDCl3) d: 1.33 (s,
-C(CH3)3, 9 protons), 3.26–3.29 (t, CH2, J ¼ 4.8 Hz, 4 protons), 3.83–
3.86 (t, CH2, J ¼ 5.1 Hz, 4 protons), 6.79 (d, Ar-H, J ¼ 9 Hz, 2 protons),
7.40 (d, Ar-H, J ¼ 8.7 Hz, 2 protons), 7.55 (d, Ar-H, J ¼ 8.7 Hz, 4 protons).
Elemental Anal. Calcd. For C26H25N5O: C, 73.74; H, 5.95; N, 16.54.
Found: C, 73.52; H, 5.80; N, 16.65.
3. Synthesis Tetrapyrazinoporphyrazine Metal Complexes
3.1. Porphyrazine Magnesium Complex (3)
Absolute n-buthanol was refluxed with magnesium (0.15 g, 6.17 mmol)
and a small crystal of iodine for 4 hr, and then 2 (0.8 g, 1.54 mmol) was
added and refluxing continued for next 3 hr. Aqueous acetic acid (50%
(v=v), 50 ml) was added after evaporation of the solvent, and the sus-
pension was stirred for 30 min. Dark solid was filtered and washed
with aqueous acetic acid, water and methanol. Crude 3 was purified
by column chromatography over silica gel with chloroform:methanol
(50:1) as eluent. 3 (dark green powder, 38%); m.p. > 300ꢀC; IR (KBr
pellet): v(cmꢁ1) 1300 (isoindole ring); 1H-NMR (300 MHz, CDCl3) d:
1.53 (broad s, -C(CH3)3, 36 protons), 3.06–4.27 (m, CH2, 32 protons),
7.06 (broad s, Ar-H, 8 protons), 7.61–8.16 (broad m, Ar-H, 24 protons).
Elemental Anal. Calcd. For C104H100MgN20O4: C, 72.69; H, 5.87; N,
16.30. Found: C, 72.57; H, 5.71; N, 16.07; MALDI-TOF-Ms spectra:
m=z 1718.8 (calcd. 1718.34).
3.2. Porphyrazine Copper Complex (4)
A mixture of 2 (1.22 g, 2.82 mmol), CuCl (0.44 g, 4.53 mmol), and a
catalytic amount of DBU (1,8-diazabicyclo[5,4,0]-7-undecene) in 12 ml
o-dichlorobenzene was heated at 180–200ꢀC for 6 hr. The deep greenish
solution product was cooled to room temperature. The precipitate was
washed with 5% HCl aqueous solution and ammonia solution. The solid
product was washed with ethyl acetate and acetone and methanol,
repeatedly. The crude product was purified by column chromatography
chloroform:methanol (30:1) as eluent. 4 (dark blue powder, 31%);
1
m.p. > 300ꢀC; IR (KBr pellet): v(cmꢁ1) 1300 (isoindole ring); H-NMR
(300 MHz, CDCl3) d: 1.53 (broad s, –C(CH3)3, 36 protons), 3.35 (broad
s, CH2, 16 protons), 4.01 (broad s, CH2, 16 protons); 7.08 (broad s,
Ar-H, 8 protons), 7.98–8.01 (broad m, Ar-H, 24 protons).

100/[842]
S. H. Kim et al.
Elemental Anal. Calcd. For C104H100CuMgN20O4: C, 71.07; H, 5.73;
N, 15.94. Found: C, 71.00; H, 5.61; N. 15.81; MALDI-TOF-Ms spectra:
m=z 1759.1 (calcd. 1757.58).
3.3. Metal-Free Tetrapyrazinoporphyrazine (5)
Magnesium phthalocyanines (3) (0.5 g, 0.272 mmol) was dissolved
in 20 ml of chloroform and a solution of tetrahydrofuran (2.58 g,
13.6 mmol) of was added. Mixture was stirred for 30 min at room tem-
perature. After this time, solvent was evaporated and resulting solid
was washed with water, hot methanol, and hot acetone. The crude pro-
duct was purified by column chromatography chloroform:methanol
(50:1) as eluent. 5 (dark blue powder, 45%); m.p.: 235–241ꢀC; IR
(KBr pellet): v(cmꢁ1) 1300 (isoindole ring); 1H-NMR (300 MHz, CDCl3)
d: ꢁ0.72 (s, N-H, 2 protons), 1.24 (s, -C(CH3)3, 36 protons), 3.11–3.35
(m, CH2, 16 protons), 3.74–3.93 (m, CH2, 16 protons), 6.93–6.99 (broad
m, Ar-H, 8 protons), 7.43–7.53 (broad m, Ar-H, 8 protons), 7.94–8.00
(broad m, Ar-H, 16 protons);
Elemental Anal. Calcd. For C104H102N20O4: C, 73.65; H, 6.06; N,
16.52. Found: C, 73.49; H, 5.98; N, 16.41; MALDI-TOF-Ms spectra:
m=z 1697.0 (calcd. 1696.05).
RESULTS AND DISCUSSION
1. Synthesis
The 1-(4-bromophenyl)-2-(4-tert-butylphenyl)ethan-1,2-dione was
synthesized by a method described in the literature [5].
CuI-catalyzed Ullmann-type reaction of electron-deficient aryl
halides with aliphatic amines occurs at 40 ꢂ 90ꢀC under the promotion
of L-proline [6]. Using L-proline as the promoter, the coupling of 1-(4-
bromophenyl)-2-(4-tert-butylphenyl)ethan-1,2-dione with morpholine
(1.5 eq) in DMSO gave 1-(4-morpolinophenyl)-2-(4-tert-butylphenyl)
ethan-1,2-dione in 56% yield.
However, due to the similar structure with phthalocyanine, synth-
esis of the tetrapyrazinoporphyrazines proceeded in a similar manner,
prepared predominantly by cyclization reactions of substituted precur-
sors of 2,3-dicyanopyrazines. The tetrapyrazinoporphyrazine precursor
(2) was synthesized from reaction of the unsymmetrical a-diketone (1)
and diaminomaleonitrile, in the presence of a catalytic amount of
p-toluenesulfonic acid in methanol.
The tetrapyrazinoporphyrazine magnesium complexes (3) were suc-
cessfully synthesized using excess magnesium butoxide in n-butanol
under reflux. When required, these magnesium complexes were easily

Characterization of Novel Tetrapyrazinoporphyrazine Derivatives 101/[843]
demetalated by stirring in excess p-toluenesulfonic acid, in THF, at
room temperature, for 30 min, to produce 5 (in a yield range of 45 ꢁ
48%). Copper complexes (4) were also prepared by using excess
cuprous chloride and DBU (1,8-diazabicyclo[5,4,0]-7-undecene) as a
catalyst in o-dichlorobenzene at refluxing conditions. The synthetic
route of this work is summarized in Scheme 1. The new compounds
were characterized by FT-IR, UV-visible spectroscopy, MALDI-TOF-
1
Ms, and H-NMR spectroscopy.
From the FT-IR spectra of diketone (1) and dicyanopyrazine com-
pound (2), the absorption band at 1677 cmꢁ1 was characteristic of dike-
tone, and the stretching vibrations of cyano group were also observed
at 2232 cmꢁ1. The strong bands at 1300 cmꢁ1 for 3 ꢂ 5 were character-
istic of the isoindole ring, with a large contribution of the C-N stretch-
ing in the inner ring and the characteristic bands remaining.
SCHEME 1 Reaction routes of tetrapyrazinoporphyrazine derivatives.

102/[844]
S. H. Kim et al.
Tetrapyrazinoporphyrazines 3 and 5 displayed a single peak at
m=z ¼ 1718.8 and 1697.0, respectively, corresponding to [M]þ in the
MALDI-TOF Ms spectra.
The 1H-NMR spectra of tetrapyrazinoporphyrazines showed a broad
peak in the corresponding range in CDCl3 due to molecular aggrega-
tion, which is frequently encountered at concentrations used for
NMR measurements. The proton absorption of the tert-butyl group
was detected at 1.53 ppm in the 1H-NMR spectrum of 3 and 4, in CDCl3.
The inner NH protons of 5 are also very well characterized by 1H-NMR,
showing a peak at ꢁ0.72 ppm as a result of the magnetic anisotropy cre-
ated by the 18 p-electron system of the phthalocyanine ring.
3.2. Electronic Spectra and Aggregation Behavior
Table 1 shows the maximum absorption wavelength and molar
absorptivity (e) values for tetrapyrazinoporphyrazines 3, 4, and 5 in
CHCl3. The ground state electronic spectra of the metal complexes
showed characteristic absorption in the Q-band region at 665 nm for
3 and 669 nm for 4. The B-band region was observed at 385 nm in
CHCl3. Compound 3 showed the highest molar absorptivity of all of
the products. The B-bands were broaden due to the superimposition
of the B1 and B2 bands. The Q-band, as well as the B-band, is a p-pꢃ
transition [7].
The metal-free phthalocyanine gives a doublet (Qx=Qy) with Q-bands
as a result of the D2h symmetry [8]. However, the absorption spectra of
5 did not show split Qx=Qy bands, as shown in Figure 1, due to the elec-
tronic coupling between a pair (or more) of porphyrazine units [9].
The aggregation behavior of phthalocyanines is a specific property
due to the intermolecular stacking of the planar and rigid core struc-
tures of the molecules. Tetrapyrazinoporphyrazine molecules become
disaggregated through solvent polarity and bulky substituent groups
[10,11]. The steric hindrance of the peripheral bulky tert-butyl group
makes solubility possible in various organic solvents such as DMF,
TABLE 1 Absorption and Molar Absorptivity of Tetrapyrazinoporphyrazines
of 3, 4, and 5 in CHCl3 (1.94 ꢄ 10ꢁ5 M)
kmax (nm)
Compd.
M
Soret band
Q-band
e(l=molꢅcm)
3
4
5
Mg
Cu
2H
385
384
386
665
669
683
6.53 ꢄ 104
5.89 ꢄ 104
4.62 ꢄ 104

Characterization of Novel Tetrapyrazinoporphyrazine Derivatives 103/[845]
FIGURE 1 Absorption spectra of 5 in DMSO, CHCl3, Toluene, and 1,4-dioxane.
DMSO, CHCl3, THF, and 1,4-dioxane. While compounds 3 and 5 did
not showed aggregation in DMSO, they did show aggregation in
CHCl3, 1,4-dioxane, and toluene, as judged by the broadening of the
Q-band, Figures 1 and 2. DMSO is a strong coordinating solvent since
they are known as the aggregation preventing solvent. And the change
of the nature of a complexed ion in the cavity has an effect on the
aggregative interaction [12]. Complex 4 did not show aggregation in
1,4-dioxane, but did show a broadness at 592 nm in CHCl3, DMSO,
and THF, suggesting aggregation (Fig. 3).
There has been a great deal of research focusing on the optical
sensitivity of phthalocyanines due to their acidic and basic properties.
The synthesized products also experienced an anion effect, especially
with the F-, Cl-, OH-, and CN- anions, which were added to the
non-aqueous solvents in the form of a tetra-n-butylammonium salt.
Previous researchers indicated that it either forms F--coordinated
complexes [13] or causes deprotonation of the proton on the pyrrole
group of metal-free phthalocyanines [14]. In our case, Figure 4 showed
the UV-visible spectral changes of 3 and 5 in chloroform upon adding
tetrabutylammonium fluoride monohydrate (TBAF). And another
experiments of other anion case such as Cl-, OH-, and CN- anions
was also carried out in other solvent THF (Fig. 5).
As the synthesized tetrapyrazinoporphyrazines added the form of
four tetra-n-butylammonium salts, the spectra of above anions were
found to change rapidly. As stated above, it showed that the anions

104/[846]
S. H. Kim et al.
FIGURE 2 Absorption spectra of 3 in DMSO, CHCl3, Toluene, and 1,4-dioxane.
could bind within the cores of the metallophthalocyanines. Isosbestic
points were observed and equilibrium mixtures of the monomer and
aggregate were included in the solution. The spectra showed a sharp
peak in the Q-band and molar absorptivity was higher than that for
the initial solution.
FIGURE 3 Absorption spectra of 4 in DMSO, CHCl3, Toluene, and 1,4-dioxane.

Characterization of Novel Tetrapyrazinoporphyrazine Derivatives 105/[847]
FIGURE 4 UV-visible absorption spectral change upon adding TBAF to 3
(1.84 ꢄ 10ꢁ5 M) and 5 (1.65 ꢄ 10ꢁ5 M).
FIGURE 5 UV-visible absorption spectral change upon adding anions (F-, Cl-,
OH-, and CN-) to 3 in THF (1.51 ꢄ 10ꢁ5 M)

106/[848]
S. H. Kim et al.
FIGURE 6 UV-visible spectral change adding upon an acid (p-toluenesufonic
acid) to 3 (1.45 ꢄ 10ꢁ5 M) and 5 (1.65 ꢄ 10ꢁ5 M)
There has also been a great deal of research focusing on the optical
sensitivity of phthalocyanines to acidic conditions. The UV-visible
spectra of the synthesized tetrapyrazinoporphyrazines in chloroform:
methanol (9:1) were measured by varying the mole ratio of tetrapyra-
zinoporphyrazines:p-toluenesulfonic acid, as shown in Figure 6. The
addition of p-toluenesulfonic acid to the chloroform:methanol (9:1)
solution of tetrapyrazinoporphyrazines resulted in reduction of aggre-
gation as evidenced by the sharp increase in Q-band intensity. When
the concentration of p-toluenesulfonic acid was increased, the absorp-
tion intensity of Q-band increased due to the electrostatic repulsion
between the morpholino group of the tetrapyrazinoporphyrazines
and the acidic group of the p-toluenesulfonic acid.
CONCLUSION
In summary, we designed and synthesized metal and metal-free
tetrapyrazinoporphyrazines bearing a morpholinophenyl substituent
as an electron donor group at the 6-position, and cyano-substituents
as electron acceptors at the 2- and 3-positions of pyrazine.
Its UV-vis absorbance were announced by changing the environment
of the molecule, for instance, organic solvent, acid, basic condition. The
aggregation behavior is a typical phenomenon of phthalocyanines and
the synthesized tetrapyrazinoporphyrazines also show aggregation
due to intermolecular p-p interactions. In our case, the optical proper-
ties of tetrapyrazinoporphyrazine derivatives was changed in control-
ling the environment of the molecules through solvent polarity and
bulky substituent groups. The synthesized products also experienced

Characterization of Novel Tetrapyrazinoporphyrazine Derivatives 107/[849]
an anion effect containing the F-, Cl-, OH-, and CN- anions. As
the synthesized tetrapyrazinoporphyrazines added the form of a
tetra-n-butylammonium salt, the spectra were found to change rapidly.
It shows that the chemical sensoring ability is acceptable for these
molecules.
REFERENCES
[1] Piechocki, C., Simon, J., Skoulios, A., Guillon, D., & Weber, P. (1982). J. Am. Chem.
Soc., 104(19), 5245–7.
[2] Enkelkamp, H. & Nolte, R. J. M. (2000). J. Porphyrins Phthalocyanines, 4, 454–459.
[3] (a) Dini, D., Hanack, M., & Meneghetti, M. (2005). J. Phys. Chem., B., 109, 12691–
12696; (b) Dini, D., Hanack, M., Egelhaaf, H., Sancha-Garcia, J. C., & Cornil, J.
(2005). J. Phys. Chem. B., 109, 5425–5432; (c) Donzello, M. P., Ou, Z., Monacelli,
F., Ricciardi, G., Rizzoli, C., Ercolani, C., & Kadish, K. M. (2005). Inorg. Chem.,
44, 9862–9873; (d) Kudrik, E. V., Theodoridis, A., Van Eldik, R., & Makarov, S. V.
(2005). Dalton Trans., 1117–1122.
[4] (a) Lee, B. H. & Jaung, J. Y. (2003). Dyes and Pigments, 59(2), 135; (b) Jaung, J. Y.
(2004). Bull. Kor. Chem. Soc., 25(10), 1453; (c) Jaung, J. Y. (2007). Dyes and
Pigments, 75(2), 420.
[5] Lee, B. H., Jaung, J. Y., Jang, S. C., & Yi, S. C. (2005). Dyes and Pigments, 65,
159–167.
[6] Zhang, H., Cai, Q., & Ma, D. J. (2005). Org. Chem., 70, 5164–5173.
[7] Piechocki, C., Simon, J., Skoulios, A., Cuillon, D., & Weber, P. (1982). J. Am. Chem.
Soc., 104, 5245.
[8] Stillman, M. J. & Nyokong, T. (1989). In: Phthalocyanines: Properties and Applica-
tions, Leznoff, C. C. & Lever, A. B. P. (Eds.), VCH: New York, chapter 3, vol. 1.
[9] Mizuguchi, J., Rihs, G.,
& Karfunkel, H. R. (1995). Solid-State Spectra of
Titanylphthalocyanine As Viewed from Molecular Distortion, Journal of Physical
Chemistry, 99(44), 16217–27.
[10] Pawlowski, G. & Hanack, M. (1980). Synthesis, 28.
[11] Wie, S., Huang, D., Li, L., & Meng, Q. (2003). Dyes and Pigments, 56(1), 1–6.
[12] Kadish, K. M., Guilard, R., & Smith, K. M. (Eds.) (2000). The Porphyrin Handbook,
Academic Press: San Diego, vol. 17.
[13] Ou, Z., Shen, J., & Kadish, K. M. (2006). Inorg. Chem., 45, 9569–79.
[14] Weitman, H., Schatz, S., Gottlieb, H. E., Kobayashi, N., & Ehrenberg, B. (2001).
Photochemisry and Photobiology, 73(5), 473–481.