Synthesis and properties of lanthanide complexes with tetrapyrazinoporphyrazine and its substituted derivatives

Article abstract of DOI:10.1134/S1070363207110175

Reactions of dicyanopyrazine and its tert-butyl-, diphenyl-, and dipyridyl-substituted derivatives with erbium, thulium, ytterbium, and lutetium chlorides, acetates, and acetylacetonates gave the corresponding tetrapyrazinoporphyrazine metal complexes which were characterized by elemental analyses, and IR, ¹H NMR, and electronic absorption spectra. The stability of the complexes to thermooxidative decomposition in air was also studied.

Full text of DOI:10.1134/S1070363207110175

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 11, pp. 1944 1950.
Original Russian Text T.A. Lebedeva, V.P. Kulinich, G.P. Shaposhnikov, S.V. Efimova, A.B. Korzhenevskii, O.I. Koifman, 2007, published in Zhurnal
Obshchei Khimii, 2007, Vol. 77, No. 11, pp. 1893 1899.
Pleiades Publishing, Ltd., 2007.
Synthesis and Properties of Lanthanide Complexes
with Tetrapyrazinoporphyrazine and Its Substituted Derivatives
T. A. Lebedeva, V. P. Kulinich, G. P. Shaposhnikov,
S. V. Efimova, A. B. Korzhenevskii, and O. I. Koifman
Ivanovo State University of Chemical Technology,
pr. F. Engel’sa 7, Ivanovo, 153460 Russia
e-mail: ttos@isuct.ru
Received January 22, 2007
Abstract Reactions of dicyanopyrazine and its tert-butyl-, diphenyl-, and dipyridyl-substituted derivatives
with erbium, thulium, ytterbium, and lutetium chlorides, acetates, and acetylacetonates gave the corresponding
tetrapyrazinoporphyrazine metal complexes which were characterized by elemental analyses, and IR, 1H
NMR, and electronic absorption spectra. The stability of the complexes to thermooxidative decomposition in
air was also studied.
DOI: 10.1134/S1070363207110175
Among numerous compounds of the porphyrazine
series, phthalocyanine derivatives have been studied
most thoroughly; some of these have found applica-
tion as light-resistant dyes and pigments, redox ca-
talysts, photosensitizers for the treatment of oncolo-
gical diseases, etc. [1 3]. Porphyrazine derivatives in
which the pyrrole rings are fused to other heterorings,
in particular tetrapyridino- and tetrapyrazinoporphyra-
zines and their substituted analogs [4 7] attract speci-
fic interest. Their coordination compounds with ter-
and quatervalent metals, such as lanthanides have
been studied to a lesser extent. Interest in porphyra-
zine complexes with lanthanides results from their
specific structure and properties, e.g., electrochromism,
sensitivity to various gases, biological activity, etc.
[8, 9]. For example, we were the first to reveal near-
IR luminescence of ytterbium complexes with octa-
phenylporphyrazine and its tert-butyl-substituted
analog [10, 11].
In the present article we report on the synthesis and
properties of erbium, ytterbium, thulium, and lutetium
complexes with tetrapyrazinoporphyrazine and its tert-
butyl-, phenyl-, and 2-pyridyl-substituted derivatives,
which contain chloride, acetate, and acetylacetonate
ions as extra ligands.
R2
R1
L
R1
N
N
N
R2
N
N
R1
N
N
CN
CN
N
N
N
N
ML3
M
N
N
N
R2
R2
N
N
N
R1
N
R1
R2
I XV
I VI, R1 = R2 = H; VII X, R1 = H, R2 = t-Bu; XI XIII, R1 = R2 = Ph; XIV, XV, R1 = R2 = pyridin-2-yl; I, II, L = Cl ;
III, IV, L = AcO ; V XV, L = acac ; I, III, V, VII, XIV, M = Er; II, IV, VI, X, XIII, M = Lu; VIII, XI, M = Tm; IX,
XII, XV, M = Yb.
1944

SYNTHESIS AND PROPERTIES OF LANTHANIDE COMPLEXES
1945
Initial 2,3-dicyanopyrazine and its substituted
derivatives were synthesized according to the known
procedures [12 15]. Metal complexes I IV were ob-
tained by the template method, i.e., by reaction of 2,3-
dicyanopyrazine with 1.5 equiv of erbium or lutetium
chloride or acetate at 200 210 C (reaction time
30 min). However, this procedure turned out to be
inapplicable for the synthesis of complexes V XV
containing acetylacetonate ion as extra ligand, for the
latter was not detected by analysis of the obtained
complexes. Therefore, complexes V XV were pre-
pared by heating a mixture of the corresponding di-
nitrile, lanthanide acetylacetonate, and urea in a high-
boling organic solvent (o-dichlorobenzene or benzo-
nitrile) at 140 160 C. As noted in [16, 17], reactions
of some dinitriles with ammonia formed as a result of
decomposition of urea during the process or upon
preliminary treatment of dinitriles with ammonia in
methanolic sodium methoxide are accompanied by
formation of compounds XVI which exist as two
tautomers. The latter undergo cyclocondensation and
complex formation at a lower temperature than in the
synthesis with the corresponding dinitriles.
NH
NH
NH2
NH
NH
NH
CN
NH3
A
A
A
CN
XVI
tert-Butyl-substituted
complexes VII X containing acetylacetonate ion as
tetrapyrazinoporphyrazine
extra ligand were synthesized in two ways according
to the scheme shown below.
NH
N
t-Bu
N
N
t-Bu
N
CN
CN
NH3
N
M(acac)3
NH2
t-Bu
t-Bu
acac
N
N
N
N
N
N
N
N
Bu-t
Bu-t
NH
N
N
N
N
N
N
N
N
N
M(acac)3
M
N
N
N
N
HN
N
N
N
t-Bu
t-Bu
N
N
N
N
N
N
Bu-t
Bu-t
XVII
VII X
Complexes VII X were isolated in the purest form
in the reactions of preliminarily prepared tetra(5-tert-
butylpyrazino)porphyrazine (XVII) [18] with lantha-
nide acetylacetonates in an aprotic organic solvent,
e.g., in pyridine or DMF. Complex formation oc-
curred even at room temperature, but the highest
yields of VII X were attained in boiling DMF (reac-
tion time 15 min).
Complexes I XV were purified by different
methods. Compounds I IV were preliminarily washed
with water and weakly polar organic solvents. All
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

1946
LEBEDEVA et al.
2
1
11 10 9 8 7 6 5 4 3 2 1 0 1 2
14 12 10 8
6
4
2
0
2
4
, ppm
, ppm
1
Fig. 1. H NMR spectra of (1) compound XVIII and (2) complex X.
complexes, except for I and II, were then subjected to
chromatographic purification on silica gel or alu-
minum oxide using chloroform, dimethylformamide,
or aqueous dimethylformamide (1:1) as eluent.
Compounds I XV are dark green powders that are
insoluble in water and soluble in DMF. It should be
noted that the presence of acetylacetonate ion as extra
ligand makes the complexes soluble in acetone,
benzene, chloroform, and other organic solvents.
Complexes I XV were identified by the data of
pletely even by heating under reduced pressure in the
presence of dehydrating agents. This may be the
reason for the observed difference between the cal-
culated and experimental elemental compositions,
which sometimes reaches 2% for some elements.
The IR spectra of metal complexes I XV contain
broadened absorption bands in the region 400 1700
1
cm ; some of these bands are typical of tetrapyrazi-
noporphyrazine metal complexes [20]. The spectra of
complexes having a chloride ion as extra ligand are
less resolved than those of the other complexes, which
suggests stronger intermolecular interactions. The
presence of acetate and acetylacetonate ligands in
complexes III XV is confirmed by the appearance in
their IR spectra of characteristic bands belonging to
stretching vibrations of aliphatic C H bonds at 2851
1
elemental analysis and IR, H NMR, and electronic
absorption spectroscopy.
Metal complexes derived from tetrapyrazinopor-
phyrazine and other aza analogs of phthalocyanine are
prone to form hydrates. As shown in [19], in some
cases crystallization water cannot be removed com-
1
and 2948 cm . The spectra lack purely carbonyl
1
bands in the region 1790 1800 cm ; instead, two
Table 1. Positions of bands in the electronic absorption
spectra of complexes I XV in DMF
1
bands at 1618 and 1354 1358 cm are observed,
which indicate metal coordination at the oxygen atom
[21].
Comp.
no.
Relative
intensity
1
max, nm (log )
Figure 1 shows the H NMR spectra of free tetra-
pyrazinoporphyrazine ligand XVII and its lutetium
complex X. It is seen that complex formation leads to
appreciable changes in the spectral pattern. The spec-
trum of complex X contains no signal at 1.6 ppm
typical of inner NH protons in the ligand. Differences
are also observed in the aliphatic region ( 1.2
1.5 ppm). In particular, the signal from protons in the
tert-butyl groups is displaced downfield by 0.5 ppm,
and a new signal appears at 1.24 ppm, which is
likely to belong to protons of the acetylacetonate extra
ligand. Aromatic protons in the ligand resonated at
8.9 ppm, but no such signal was present in the spec-
trum of complex X, presumably due to effect lutetium
ion coordinated to acetylacetonate ion [22].
I
II
III
IV
V
637, 592, 367
639, 581, 339
638, 581, 368
1:0.23:0.47
1:0.28:0.51
1:0.31:0.50
1:0.25:0.43
637, 590, 357
638 (4.18), 580 (3.59), 337 (3.99)
638, 581, 365
VI
1:0.26:0.43
VII 640 (4.92), 582 (4.23), 367 (4.69)
VIII 642 (4.91), 583 (4.22), 339 (4.67)
IX
X
XI
633 (4.92), 578 (4.21), 339 (4.67)
640 (4.91), 584 (4.22), 341 (4.68)
660 (4.16), 602 (3.61), 367 (3.95)
659, 602, 367
XII
XIII
1:0.34:0.57
1:0.33:0.45
657, 598, 367
XIV 660 (4.17), 600 (3.65), 370 (3.96)
XV 657, 600, 368
All complexes I XV displayed in the electronic
absorption spectra (Table 1, Figs. 2, 3) a strong Q
band in the long-wave region ( 633 660 nm); a
1:0.19:0.35
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

SYNTHESIS AND PROPERTIES OF LANTHANIDE COMPLEXES
1947
D
D
1.0
1.0
1
0.8
687
684
682
657
0.6
0.4
4
0.5
3
0.2
0.0
2
2
1
400
500 600
700
800
900
, nm
0.0
400
500
600
700
800
, nm
Fig. 2. Electronic absorption spectra of complex XV in
(1) DMF and (2) 5, (3) 10, and (4) 20% hydrochloric
acid.
Fig. 3. Electronic absorption spectra of (1) compound
XVII and (2) complex VII in chloroform.
shoulder or a weak satellite band was observed on the
short-wave slope of the Q band. Also, the Soret band
was present in the UV region ( 339 370 nm). The
positions of these bands depend on the nature of the
metal and extra ligand. Peripheral substituents also
affect the electronic absorption spectra to an ap-
preciable extent. Introduction of eight aromatic phenyl
or 2-pyridyl substituents leads to a red shift of the Q
composition. The results are collected in Table 2.
Decomposition of complexes, which is accompanied
by weight loss and exothermic effects, starts at a
temperature above 350 C. It is seen that the tempera-
ture range corresponding to the maximal rate of
weight loss and maximal exothermic effect in the
series of tetrapyrazinoporphyrazine erbium complexes
strongly depend on the extra ligand nature. The most
thermally stable is chloride complex I, while acetate
and acetylacetonate complexes are less stable. The
latter are characterized by a more complicated shape
of the DTA curve. Complexes V, VI, and X showed
two exothermic peaks at 400 420 C and 440 475 C,
indicating that the process includes successive de-
composition of the acetylacetonate extra ligand and
tetrapyrazinoporphyrazine macroring. In going from
unsubstituted acetylacetonate tetrapyrazinoporphyra-
zine lutetium complex VI to its tert-butyl-substituted
analog X, the temperature corresponding to the
band (
15 20 nm). Formalistically, these aromatic
fragments are not conjugated with the macroring;
nevertheless, they contribute to some extent to the
entire aromatic system. Analogous variations were
observed by us previously in going, e.g., from tetra-
azaporphyrins to their octaphenyl-substituted deri-
vatives [23]. Introduction of tert-butyl groups into the
pyrazine rings considerably increases the solubility
but almost does not affect the electronic absorption
spectra. The position of the Q band changes by only
1 3 nm.
Octapyridyl-substituted complexes XIV and XV
are readily soluble in hydrochloric acid over a wide
concentration range due to the presence of pyridine
fragments capable of forming salts with acids. In the
electronic absorption spectra of solutions of these
complexes in hydrochloric acid, the strong Q band
and its satellite are conserved, but their position
changes by 25 30 nm (bathochromic shift) relative to
the spectra in DMF. The bathochromic shift increases
as the concentration of hydrochloric acid rises.
Table 2. Parameters of thermooxidative decomposition of
tetrapyrazinoporphyrazine erbium and lutetium complexes
Temperature,
C
Comp.
no.
maximal exothermic
effect
maximal weight loss
I
III
V
VI
X
500
462
400, 464
400, 475
400, 450
510
462
400, 464
400, 475
400 420, 440
Taking into account that the obtained tetrapyra-
zinoporphyrazine were planned to be used at elevated
temperature in the presence of atmospheric oxygen,
we examined their stability to thermooxidative de-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

1948
LEBEDEVA et al.
maximal weight loss and maximal exothermic effect
decreases by 25 35 C.
%: C 40.6; H 1.7; N 28,7; O 4.6. C26H11ErN16O2.
Calculated, %: C 41.8; N 1.5; N.0; O 4.3.
We can conclude that the newly synthesized com-
plexes are quite stable toward termooxidative de-
composition and that their stability is determined
primarily by the nature of the extra ligand and peri-
pheral substituents.
Acetato(tetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)lutetium(III) (IV) was synthesized
in a similar way from 0.4 mmol of dicyanopyrazine
and 0.15 mmol of lutetium acetate tetrahydrate. Yield
1
8 mg (11%). IR spectrum, , cm : 1524 (C=C), 1651
(C=N), 2854 (C Has, Ac), 2924 (C Hs, Ac). Found,
%: C 40.2; H 1.7; N 28,6; O 4.7. C26H11N16O2Lu.
Calculated, %: C 41.4; H 1.5; N 29.7; O 4.2.
EXPERIMENTAL
The electronic absorption spectra were measured
in the region from 300 to 900 nm on a Hitachi U-
2001 spectrophotometer at room temperature from
solutions in DMF, chloroform, and 5, 10, and 20%
hydrochloric acid. The IR spectra were recorded in
KBr on an Avatar 360 FT-IR ESP spectrometer. The
elemental compositions were determined using a
Acetylacetonato(tetrapyrazino[b,g,l,q]-5,10,15,20-
tetraazaporphyrinato)erbium(III) (V). A quartz
ampule was charged with 0.4 mmol of dicyanopyra-
zine and 0.15 mmol of tris(acetylacetonato)erbium(III),
15 ml of benzonitrile, 1.6 mmol of urea, and a ca-
talytic amount of sodium methoxide were added in
succession, and the mixture was heated to 160 C and
kept for 1 h at that temperature. The mixture was then
filtered while hot, benzonitrile was distilled off from
the filtrate under reduced pressure, and the residue
was purified by column chromatography on aluminum
oxide (Brockmann activity grade I; DMF water, 1:1).
1
Flash EA Series 1112 CHNS-O analyzer. The H
NMR spectra were recorded on a Bruker AMD 200.
Thermogravimetric studies were performed on a
1000D Derivatograph (MOM, Hungary) equipped
with a programmable setup for signal measurement
[24].
1
Yield 24 mg (30%). IR spectrum, , cm : 1660
(C=N), 2852 (C Has, acac), 2926 (C Hs, acac).
Found, %: C 44.0; H 2.0; N 28.0; O 4.2. C29H15Er
N16O2. Calculated, %: C 44.3; H 1.9; N 28.5; O 4.1.
Chloro(tetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)erbium(III) (I). A mixture of
0.4 mmol of dicyanopyrazine and 0.15 mmol of er-
bium(III) chloride was heated for 30 min at 200
210 C in quartz ampule. The ampule was cooled, and
the product was withdrawn therefrom, finely ground,
and washed with water until the absence of chloride
ions in the washings. The product was additionally
purified by removal of impurities by Soxhlet extrac-
tion with ethanol. Yield 24 mg (33%). IR spectrum,
Acetylacetonato(tetrapyrazino[b,g,l,q]-5,10,15,20-
tetraazaporphyrinato)lutetium(III) (VI) was syn-
thesized in a similar way from 0.4 mmol of dicyano-
pyrazine and 0.15 mmol of tris(acetylacetonato)lute-
1
tium(III). Yield 26 mg (33%). IR spectrum, , cm :
1660 (C=N), 2852 (C Has, acac), 2926 (C Hs, acac).
Found, %: C 43.1; H 2.0; N 28.0; 4.1. C29H17Lu
N16O2. Calculated, %: C 43.9; H 1.9; N 28.2; O 4.0.
1
, cm : 1383, 1527 (C=C), 1651 (C=N). Found, %:
C 38.1; H 1.2; N 29.8. C24H8ClErN16. Calculated,
%: C 39.9; H 1.1; N 31.0.
Acetylacetonato(22,72,122,172-tetra-tert-butyl-
tetrapyrazino[b,g,l,q]-5,10,15,20-tetraazaporphyri-
nato)erbium(III) (VII). A solution of 0.1 mmol of
tetra(5-tert-butylpyrazino)porphyrazine and 1.5 mmol
of tris(acetylacetonato)erbium(III) in dimethylform-
amide was heated to the boiling point and was kept
for 15 min at that temperature. The solvent was
evaporated, and the residue was purified by column
chromatography on silica gel L 100/250 using chloro-
form as eluent. Yield 67 mg (66%). IR spectrum, ,
Chloro(tetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)lutetium(III) (II) was synthesized
in a similar way from 0.4 mmol of dicyanopyrazine
and 0.15 mmol of lutetium(III) chloride. Yield 23 mg
1
(31%). IR spectrum, , cm : 1384, 1528 (C=C), 1651
(C=N). Found, %: C 38.2; H 1.2; N 29.1. C24H8Cl^
LuN16. Calculated, %: C 39.5; H 1.1; N 30.7.
Acetato(tetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)erbium(III) (III) was synthesized
in a similar way from 0.4 mmol of dicyanopyrazine
and 0.15 mmol of erbium(III) acetate tetrahydrate.
The product was additionally purified by column
chromatography on aluminum oxide (Brockmann
activity grade I; DMF water, 1:1). Yield 15 mg
1
cm : 1633 (C=N), 2960 (C Has), 2854 (C Hs).
Found, %: C 53.9; H 4.9; N 22.1; O 3.2. C45H49Er
N16O2. Calculated, %: C 53.3; H 4.8; N 22.1; O 3.2.
Acetylacetonato(22,72,122,172-tetra-tert-butyl-
tetrapyrazino[b,g,l,q]-5,10,15,20-tetraazaporphyri-
nato)thulium(III) (VIII) was synthesized in a similar
way from 0.1 mmol of tetra(5-tert-butylpyrazino)-
porphyrazine and 0.15 mmol of tris(acetylacetonato)-
1
(21%). IR spectrum, , cm : 1524 (C=C), 1647
(C=N), 2852 (C Has, Ac), 2921 (C Hs, Ac). Found,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 11 2007

SYNTHESIS AND PROPERTIES OF LANTHANIDE COMPLEXES
1949
1
thulium(III). Yield 62 mg (59%). IR spectrum,
,
Yield 205 mg (88%). IR spectrum, , cm : 1397,
1599 (C=C); 1652 (C=N); 2859 (C Has, acac); 2933
(C Hs, acac). Found, %: C 64.2; H 3.7; N 14.6; O 2.4.
C77H47LuN16O2. Calculated, %: C 65.9; H 3.3; N 15.9;
O 2.3.
1
cm : 1637 (C=N), 2958 (C Has), 2857 (C Hs).
Found, %: C 53.1; H 4.7; N 22.1; O 2.9. C45H49N16
O2Tm. Calculated, %: C 53.2; H 4.8; N 22.1; O 3.1.
Acetylacetonato(22,72,122,172-tetra-tert-butyl-
tetrapyrazino[b,g,l,q]-5,10,15,20-tetraazaporphyri-
nato)ytterbium(III) (IX) was synthesized in a similar
way from 0.1 mmol of tetra(5-tert-butylpyrazino)-
porphyrazine and 0.15 mmol of tris(acetylacetonato)-
Acetylacetonato[22,23,72,73,122,123,172,173-
octakis(pyridin-2-yl)tetrapyrazino[b,g,l,q]-5,10,15,
20-tetraazaporphyrinato)erbium(III) (XIV) was
synthesized as described above for complex V from
0.80 mmol of 5,6-bis(pyridin-2-yl)pyrazine-2,3-di-
carbonitrile and 0.30 mmol of tris(acetylacetonato)-
ytterbium(III). Yield 75 mg (74%). IR spectrum,
,
1
cm : 1633 (C=N), 2951 (C Has), 2856 (C Hs).
Found, %: C 53.1; H 4.7; N 21.9; O 3.2. C45H49N16
O2Yb. Calculated, %: C 53.0; H 4.8; N 22.0; O 3.1.
1
erbium(III). Yield 76 mg (28%). IR spectrum, , cm :
1391, 1597 (C=C); 1650 (C=N); 2862 (C Has, acac);
2956 (C Hs, acac). Found, %: C 61.0; H 2.9; N 23.6;
O 2.6. C69H39ErN24O2. Calculated, %: C 58.9; H 2.8;
N 23.9; O 2.5.
Acetylacetonato(22,72,122,172-tetra-tert-butyl-
tetrapyrazino[b,g,l,q]-5,10,15,20-tetraazaporphyri-
nato)lutetium(III) (X) was synthesized and purified
as described above for complex VII from 0.1 mmol
Acetylacetonato[22,23,72,73,122,123,172,173-
octakis(pyridin-2-yl)tetrapyrazino[b,g,l,q]-5,10,15,
20-tetraazaporphyrinato)ytterbium(III) (XV) was
synthesized as described above for complex V from
0.80 mmol of 5,6-bis(pyridin-2-yl)pyrazine-2,3-dicar-
bonitrile and 0.30 mmol of tris(acetylacetonato)ytter-
of
tetra(5-tert-butylpyrazino)porphyrazine
and
0.15 mmol of tris(acetylacetonato)lutetium(III). Yield
67 mg (72%). IR spectrum, , cm : 1638 (C=N),
1
2961 (C Has), 2855 (C Hs). Found, %: C 52.2; H 4.8;
N 21.9; O 3.2. C45H49LuN16O2. Calculated, %: C
52.9; H 4.8; N 21.9; O 3.1.
1
bium. Yield 74 mg (26%). IR spectrum, , cm : 1396,
1597 (C=C); 1648 (C=N); 2863 (C Has, acac); 2959
(C Hs, acac). Found, %: C 59.1; H 2.9; N 22.9; O 2.6.
C69H39N24O2Yb. Calculated, %: C 58.7; H 2.8; N
23.8; O 2.3.
Acetylacetonato(22,23,72,73,122,123,172,173-
octaphenyltetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)thulium(III) (XI) was synthesized
as described above for complex V from 0.66 mmol of
5,6-diphenylpyrazine-2,3-dicarbonitrile and 0.16 mmol
of tris(acetylacetonato)thulium(III). The products was
purified by column chromatography on Silica gel L
40/100 using DMF as eluent. Yield 200 mg (87%). IR
REFERENCES
1. Stepanov, B.I., Vvedenie v khimiyu i tekhnologiyu
organicheskikh krasitelei (Chemistry and Technology
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2. Maizlish, V.E., Kudrik, E.V., and Shaposhnikov, G.P.,
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3. Uspekhi khimii porfirinov (Advances in the Chemistry
of Porphyrins), Golubchikov, O.A., Ed., St. Peters-
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Univ., 1997, p. 357.
1
spectrum, , cm : 1397, 1599 (C=C); 1652 (C=N);
2859 (C Has, acac); 2933 (C Hs, acac). Found, %:
C 65.1; H 3.5; N 15.9; O 2.4. C77H47N16O2Tm.
Calculated, %: C 66.2; H 3.3; N 16.1; O 2.3.
Acetylacetonato(22,23,72,73,122,123,172,173-
octaphenyltetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)ytterbium(III) (XII) was synthe-
sized as described above for complex XI from
0.41 mmol of 5,6-diphenylpyrazine-2,3-dicarbonitrile
and 0.14 mmol of tris(acetylacetonato)ytterbium(III).
4. Surov, I.V. and Berezin, D.B., Izv. Vyssh. Uchebn.
Zaved., Khim. Khim. Tekhnol., 1998, vol. 31,
no. 7, p. 34.
1
Yield 120 mg (84%). IR spectrum, , cm : 1394,
1593 (C=C); 1642 (C=N); 2853 (C Has, acac); 2963
(C Hs, acac). Found, %: C 65.9; H 4.1; N 17.2; O 2.7.
C77H47N16O2Yb. Calculated, %: C 66.1; H 3.4; N
16.2; O 2.3.
5. Maizlish, V.E., Korzhenevskii, A.B., and Klyu-
ev, V.N., Khim. Geterotsikl. Soedin., 1984, no. 9,
p. 1257.
6. Kudrik, E.V., Shishkin, V.N., and Shaposhnikov, G.P.,
Koord. Khim., 2005, vol. 31, no. 7, p. 530.
Acetylacetonato(22,23,72,73,122,123,172,173-
octaphenyltetrapyrazino[b,g,l,q]-5,10,15,20-tetra-
azaporphyrinato)lutetium(III) (XIII) was synthe-
sized as described above for complex XI from
0.66 mmol of 5,6-diphenylpyrazine-2,3-dicarbonitrile
and 0.16 mmol of tris(acetylacetonato)lutetium(III).
7. Gal’pern, M.G., Kudrevich, S.V., and Novozhi-
lov, I.G., Khim. Geterotsikl. Soedin., 1993, no. 1,
p. 58.
8. Kulinich, V.P. and Shaposhnikov, G.P., Russ. J. Gen.
Chem., 2003, vol. 73, no. 5, p. 794.
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