Mendeleev
Communications
Mendeleev Commun., 2008, 18, 82–83
Synthesis and properties of [4'-(p-triphenylmethylphenoxy)-
7,8:12,13:17,18-tribenzoporphyrazinato]nickel(II)
Yulia V. Romanenko, Elena A. Danilova, Olga G. Khelevina and Mikhail K. Islyaikin*
Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russian Federation.
Fax: +7 4932 41 7742; e-mail: islyaikin@isuct.ru
DOI: 10.1016/j.mencom.2008.03.009
A new noncentrosymmetric structural analogue of phthalocyanine, [4'-(p-triphenylmethylphenoxy)-7,8:12,13:17,18-tribenzo-
porphyrazinato]nickel(II), was obtained by the condensation of 3,5-bis(1-imino-3-isoindolinylidenamino)-1,2,4-triazole in the
presence of Ni(OAc)2·4H2O or a Ni complex of 3,5-bis(1-imino-3-isoindolinylidenamino)-1,2,4-triazole with 4-(p-tri-
phenylmethylphenoxy)phthalonitrile.
Noncentrosymmetrical structural phthalocyanine analogues are
NC
CN
N
NH
of interest1 because they can form Langmuir–Blodgett layers2
and reveal interesting coordination3 and nonlinear optical
properties.4
N
N
N
A
NH
HN
HN
+
We synthesised a Ni complex of triazolephthalocyanine,
[4'-(p-triphenylmethylphenoxy)-7,8:12,13:17,18-tribenzoporphyr-
azinato]nickel(II) 1,† which is a structural analogue of phthalo-
cyanine.
O
CPh3
NH
Ni(OAc)2
EtOC2H4OH
2
3
1
N
N
NC
+
CN
O
N
NH
N
N
N
N
N
N
PhOH
CPh3
...
...
N
N
Ni
N
N
Ni
N
B
OH
2 HN
N
N
NH
4
3
Scheme 1
of Ni(OAc)2·4H2O in ethoxyethanol and (B) the interaction of
Ni complex 4 with 3 in phenol (Scheme 1).†
O
CPh3
Taking into account the low stability of the products7 under
the reaction conditions, the synthesis was carried out at 50 °C
for 100 h (method A). The use of Ni complex 4 allows us to
increase the temperature and to reduce the duration of synthesis
(method B). Phenol used as a solvent in this case transforms
phthalonitrile into more reactive phenoxy derivatives8 and prevents
phthalocyanine formation.
The dark brown compounds obtained after extraction and
column chromatography were slightly soluble in CHCl3 and DMF
and almost insoluble in pyridine.
1
The synthesis of 1 was carried out by (A) the condensation
of 3,5-bis(1-imino-3-isoindolinylidenamino)-1,2,4-triazole5 2 with
4-(p-triphenylmethylphenoxy)phthalonitrile6 3 in the presence
†
Synthesis of [4'-(p-triphenylmethylphenoxy)-7,8:12,13:17,18-tribenzo-
porphyrazinato]nickel(II) 1.
(A) A mixture of 3,5-bis(1-imino-3-isoindolinylidenamino)-1,2,4-tri-
azole 2 (0.33 g, 0.92 mmol), 4-(p-triphenylmethylphenoxy)phthalonitrile6
3 (0.42 g, 0.92 mmol) and nickel(II) acetate tetrahydrate (0.23 g, 0.92 mmol)
in 2-ethoxyethanol (40 ml) was stirred at 50 °C for 100 h. The solvent
was removed in a vacuum, and the crude product was washed with hot
MeOH and then extracted with CHCl3 in a Soxhlet apparatus. After
solvent evaporation, the product was purified by column chromato-
graphy on silica gel (CHCl3–MeOH, 25:1). The solvents were removed
and the brown solid was dried in a vacuum. Yield, 0.060 g (7.7%).
(B) A mixture of compound 4 (0.38 g, 0.92 mmol), 4-(p-triphenylmethyl-
phenoxy)phthalonitrile 3 (0.42 g, 0.92 mmol) and phenol (3 g) was stirred
at 140 °C for 8 h. The reaction mass was heated to 160 °C, stirred at this
temperature for 2 h and then poured into water. The residue was filtered
and washed with water and acetone to remove phenol. A crude product
was purified as described above. Yield, 0.063 g (8.0%).
The mass spectrum (MALDI-TOF) of compound 1 contains
a signal (m/z 858), which corresponds to a molecular ion
364
2.0
1.5
499
627
1.0
0.5
0.0
574
MS (MALDI-TOF, dithranol), m/z: 858 (M + H)+. UV-VIS [CHCl3,
max/nm (log e)]: 364 (4.25), 627 (3.83). IR (KBr, n/cm–1): 3084, 3055,
3029, 1664, 1612, 1594, 1471, 1444, 1400, 1323, 1088, 1048, 839, 753,
701, 653, 512. Found (%): C, 70.73; H, 3.80; N, 16.75; O, 2.04; Ni, 6.68.
Calc. for C51H30N10ONi (%): C, 71.43; H, 3.53; N, 16.33; O, 1.87; Ni, 6.84.
l
400
500
600
in CHCl3 (
700
Figure 1 UV-VIS spectrum of a solution of
1
c
= 0.136 mmol dm–3).
– 82 –
© 2008 Mendeleev Communications. All rights reserved.
Romanenko, Yulia V.
