2
O.A. Dmitrieva et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 240 (2020) 118601
+
1
z), Found 1582.926 [M+2H] , Calculated 1580.901. Н NMR (CDCl
3
) δ,
and dried in air at 70 °C. Yield: 140.0 mg (24.3%). MALDI-TOF (m/z),
+
1
ppm: 8.05 d (16H, J = 8.1 Hz, 2,6-H-Ar); 7.58 d (16H, J = 8.1 Hz, 3,5-H-
Ar); 1,48 s (72H, H-tBu); −0.66 s (2H, NH). UV–Vis spectra of the I,
max, nm (lg ε): 679 (5.28), 648 (5.18), 473 (4.83), sh, 372 (5.15) (chlo-
Found 1578.393 [M+H] , Calculated 1577.141. Н NMR (CDCl
ppm: 8.37 d (16H, J = 8.3 Hz, 2,6-H-Ar); 7.65 d (16H, J = 8.3 Hz, 3,5-
H-Ar); 1.54 s (72H, H-tBu) (CDCl ). UV–Vis λmax, nm (lg ε): 677
(4,95); 423 (4,84) (CHCl ).
3
) δ,
λ
3
roform); 464sh (4.55), 593sh (4.38), 616sh (4.48), 646 (4.97), 674
3
(
(
5.07) (acetonitrile). UV–Vis spectra of the (I)2−, λmax, nm (lg ε): 665
Bis(4-tert-butylphenyl)fumaronitrile. 4.6 g of sodium (0.2 mol) was
dissolved in methanol (75.0 ml) with stirring, and resulting solution
was gradually added while cooling (temperature below 10 °C) to a stir-
ring solution of 25.4 g iodine (0.1 mol) and 17.3 g (4-tert-butylphenyl)
acetonitrile (0.1 mol) in a mixture of methanol (70.0 ml) and ether
(375 ml). The reaction mixture was stirred for 30 min and washed 3
times with water, then evaporated to a half and cooled overnight in
the refrigerator. The precipitate was filtered off, washed with a little
amount of ether and dried. Yield: 6.20 g (36.3%). Melting point:
4.97), 603sh (4.29) (acetonitrile+DBU).
,3-Dicyano-5,6-bis(4-tert-butylphenyl)pyrazine. A solution of 4.0 g
12.4 mmol) bis(4-tert-butylphenyl)ethanedione, 1.4 g (13.0 mmol) of
diaminomaleodinitrile and 100 mg of p-toluenesulfonic acid in
5.0 ml of methanol was refluxing for 3 h, then the mixture was cooled.
The precipitate was filtered off, washed with methanol and dried in air
at room temperature. Yield 4.2 g (85.9%). Melting point: 161–165 °C.
MALDI-TOF (m/z), Found 395.667 [M+H] , Calculated 395.53.
) δ, ppm: 7.55 dt (4H, J = 8.6 Hz, J = 2.1 Hz; 2,6-H-Ar);
.41 dt (4H, J = 8.6 Hz, J = 2.1 Hz; 3,5-H-Ar); 1.35 s (18H, H-tBu).
2
(
1
+
1
Н
1
+
NMR (CDCl
7
3
222–224 °C. MALDI-TOF (m/z), Found 343.460 [M+H] , Calculated
1
1
1
343.49. Н NMR (CDCl
2
3
) δ, ppm: 7.81 dt (4H, J = 8.5 Hz, J = 2.0 Hz,
1
,6-H-Ar); 7.56 dt (4H, J = 8.5 Hz, J = 2.0 Hz, 3,5-H-Ar); 1.37 s (18H,
2
.2. Tetra(4-tert-butyl)phthalocyanine (II)
H-tBu).
The individuality of the compounds was controlled by TLC on Silufol
plates with a layer thickness of 0.5 mm (Merck), eluent: chloroform. The
purification and identification of the compound were carried out ac-
cording to [9]. Spectrophotometric titration with acetonitrile solutions
of perchloric acid in acetonitrile was carried out on Cary 100 spectro-
photometers from Varian and SPEC SSP-715. A highly purified acetoni-
trile was used as dipolar aprotic solvent (water content was b0.03%),
in which the initial objects were in molecular form, that was confirmed
by the initial spectra of porphyrins. The experimental procedure, pre-
parative chemistry, and experimental data processing are presented in
The mixture of 3.0 g 4-tert-butylphthalonitrile (16.3 mmol), 0.12 g of
lithium (17.1 mmol) and 20.0 ml of dried quinoline (as a solvent) were
refluxing for 3 h, cooled and then concentrated hydrochloric acid
30.0 ml) and water (150.0 ml) were added to the mixture with stirring.
The precipitate was filtered off, washed with water and dried. The resi-
due was dissolved in chloroform and chromatographed on alumina of
the III degree of activity with chloroform as eluent. The eluate was evap-
orated, the product was precipitated with methanol, filtered off, washed
(
with methanol and dried at 70 °C in air. Yield: 0.80 g (36.2%). R
f
1
(
7
(
−
Silufol): 0.52 (chloroform - hexane, 3:1). MALDI-TOF (m/z), Found
detail in [10–12]. Proton magnetic resonance spectra ( H NMR) were
+
1
39.156 [M] , Calculated 738.981. Н NMR (CHCl
3
) δ, ppm: 9.16 m
measured on a Bruker AV III-500 spectrophotometer (internal standard
- TMS). Mass spectra were recorded on a Shimadzu Axima Confidence
time-of-flight mass spectrometer (MALDI-TOF).
4H, 6-H); 8.86 m (4H, 3-H); 8.15 m (4H, 5-H); 1.90 m (36H, H-tBu);
2.60 bs (2H, NH) (CDCl ) (mixture of atropisomers). UV–Vis spectra
of the II, λmax, nm (lg ε): 701 (5.10), 664 (5.03), 645 (4.59), 603
3
Fluorescence properties of the free ligands (I-III) in acetonitrile and
−
2−
2−
(
6
4
4.41), 342 (4.81) (chloroform); 599 (4.21), 638sh (4.36), 661 (4.77),
their ionic forms (I2 , II and III ) in a mixture of acetonitrile-DBU
were studied at 295 K. Fluorimetric measurements of solutions of
porphyrazines were carried out on a Shimadzu RF-5301 fluorimeter.
Fluorescence was measured for highly dilute solutions (b10− mol/l)
due to possible strong reabsorption processes observed at high concen-
trations of solutions, which can often provoke a bathochromic shift of
fluorescence maxima for some phthalocyanines [13].
2−
96 (4.82) (acetonitrile). UV–Vis spectra of the (II) , λmax, nm (lgε):
00 (4.75), 608sh (4.19), 673 (4.75) (acetonitrile + DBU).
7
2
.3. Octakis(4-tert-butylphenyl)porphyrazine (III)
A solution of 0.20 g Pb-octakis(4-tert-butylphenyl)porphyrazine
(
0.13 mmol) in trifluoroacetic acid (5.0 ml) was refluxing in argon at-
The fluorescence spectra of the studied samples in toluene
were compared with standard values from literature. The
Zinc-phthalocyanine (ZnPс) was chosen as the standard, for which the
quantum yield in pyridine is known and equals to 0.3 [14]. The corre-
sponding integral fluorescence intensities were calculated. The quan-
mosphere for 1 h, then it was poured into water and concentrated am-
monia solution (5.0 ml) was added to the resulting mixture. The
precipitate was filtered off, washed with water and dried. The product
was dissolved in chloroform and chromatographed on silica gel with
chloroform as eluent. The eluate was evaporated to a minimal amount
and diluted with methanol (25.0 ml). Precipitated residue was filtered
off, washed with methanol and dried in air at 70 °C. Yield: 120.0 mg
2−
tum fluorescence yield of compounds (I-III) and their ionic forms (I
,
2
−
2−
II , III ) was calculated by the standard method [15] using a PFPC
software package v.2.04 according to formula (1):
(
67.3%). R
f
(Silufol): 0.81 (benzene-hexane, 1: 1). MALDI-TOF (m/z),
+
1
IxAstn2x
Found 1372,825 [M+Н] , Calculated 1371,950. Н NMR (CHCl
ppm: 7.81 d (2H, J = 8.1 Hz, 2,6-H-Ar); 7.56 d (2H, J = 8.1 Hz, 3,5-H-
Ar); 1.39 s (72H, tBu); 0,10 bs (2H, NH). UV–Vis spectra of the III:
3
) δ,
Q ¼ Q
x
ð1Þ
st
IstAxn2
st
λ
max, nm (lg ε): 677 (4.60), 610 (4.46), 484 (4.43), 376 (4.63) (chloro-
form); 712 (4.92), 674 (4.99), 612 (4.78), 473 (4.88), 402sh (4.79),
78 (4.91) (acetonitrile). UV–Vis spectra of the (III)2−: (λmax, nm (lg
where Q
dard, respectively; A
wavelength; I and Ist are the integrated intensities; n
x
x
and Qst are the quantum yields of the test sample and stan-
and Ast are their optical density at the excitation
and nst are the
x
3
x
ε): 672 (5.03), 614sh (4.88), 468 (4.76), 372sh (4.89), 321sh (4.99) (ace-
tonitrile + DBU).
refractive indices of the solvents for the sample and standard, respec-
tively. The error of the fluorimetric measurements was ~10%.
Pb(II)-2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)porphyrazine. A
The calculations were carried out in the GAMESS v.12 software pack-
age [16]. The BP86 functional [17,18] and the base set def2-TZVP [19]
was used for calculations. The BP86 functional provides high-precision
calculations of the geometry of tetrapyrrole macrocycles. In some
cases, this accuracy exceeds the accuracy provided by the frequently
used B3LYP method [20–23]. A complete optimization of geometry of
mixture of 0.50
g
1,2-bis(4-tert-butylphenyl)fumaronitrile
(
1.46 mmol) and 0.3 g lead acetylacetonate (0.74 mmol) was refluxing
in ethyleneglycol (20.0 ml) for 2 h. Then the mixture was cooled, the
precipitate was filtered off, washed with water and dried in air at
0 °C. The product was dissolved in methylene chloride and
chromatographed on silica gel, eluting with methylene chloride. The el-
uate was evaporated to a minimal amount and diluted with methanol
7
2
−
the free ligands (I-III) structures and their deprotonated forms (I
,
2
−
2−
II
and III ) were optimized in the ground state by DFT method.
(
25.0 ml). Precipitated residue was filtered off, washed with methanol
The results of theoretical calculation of energy levels and the