Spectral-Fluorescence Properties of Zn(II)-Octaphenyltetraazaporphyrins

Article abstract of DOI:10.1007/s10895-020-02530-1

Zn(II)-octa-(4-chlorophenyl)- and Zn(II)-octa-(4-bromophenyl)tetraazaporphyrins were synthesized by the reaction of cyclotetramerization of di-(4-chlorophenyl)- and di-(4-bromophenyl)maleonitriles with zinc(II) chloride. The obtained compounds were identi

Full text of DOI:10.1007/s10895-020-02530-1

Journal of Fluorescence
https://doi.org/10.1007/s10895-020-02530-1
ORIGINAL ARTICLE
Spectral-Fluorescence Properties of Zn(II)
-Octaphenyltetraazaporphyrins
Olga A. Dmitrieva1 & Natalya V. Chizhova1 & Alexey I. Rusanov2 & Mikhail O. Koifman2 & Nugzar Z. Mamardashvili1
Received: 30 December 2019 /Accepted: 20 March 2020
#
Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
Zn(II)-octa-(4-chlorophenyl)- and Zn(II)-octa-(4-bromophenyl)tetraazaporphyrins were synthesized by the reaction of
cyclotetramerization of di-(4-chlorophenyl)- and di-(4-bromophenyl)maleonitriles with zinc(II) chloride. The obtained com-
pounds were identified by UV-vis, IR, NMR 1H spectroscopy and mass spectrometry. Geometry optimization of the series of
halogenated Zn(II)-octaaryltetraazaporphyrins was performed using the density functional method with the BP86 functional and
the def2-TZVP basis set. An analysis of the distribution of molecular orbital energies in the neighborhood of highest occupied
molecular orbitals (HOMO and HOMO-1) and lowest unoccupied molecular orbitals (LUMO and LUMO+1) and the width of
the HOMO – LUMO energy gaps (EH-L) was performed for the studied compounds. Fluorimetric measurements of the Zn(II)-
octaphenyltetraazaporphyrins in toluene were carried out and fluorescence quantum yields of studied compounds were deter-
mined and analyzed. It has been shown that the halogen on the para-position of the phenyl groups significantly affects the value of
the obtained quantum yields of fluorescence emission but does not significantly affect the Stokes shifts.
.
.
.
Keywords Zn(II)-octaphenyltetraazaporphyrins Spectral-fluorescence properties Fluorescence quantum yield Density
.
functional theory Time-dependent density functional theory
Introduction
analytical chemistry as sensors [4–9]. Fluorescence imaging
using contrast agents is a new highly sensitive method for
detecting tumors [10, 11]. Moreover, the vast majority of
metalloporphyrin receptors are represented by zinc porphy-
rins, since these chromophores have a significant fluorescence
quantum yield and long-lived triplet states. Chemical modifi-
cation of the peripheral substituents of the macrocycle leads to
a significant change of its spectral and electrochemical prop-
erties [12, 13], making it possible to create new polyfunctional
materials with specified photophysical properties that can ex-
pand the scope of porphyrazines.
Porphyrazines or tetraazaporphyrins exhibit interesting and
unique photophysical, photochemical and electrochemical
properties. This, in turn, leads to a constant high interest in
these compounds in terms of their potential applications in the
fields of sensors, catalysts, dye sensitized solar cells and
others [1–3]. Recently, porphyrins and their aza-analogues
are widely used in photodynamic therapy and photodynamic
diagnosis as photosensitizers, in chemical catalysis, and in
In this work, complexes of Zn(II) with octa-(4-
chlorophenyl)- and octa-(4-bromophenyl)-tetraazaporphyrins
were synthesized by the reaction of cyclotetramerization of
di-(4-chlorophenyl)- and di-(4-bromophenyl)maleonitriles
with zinc(II) chloride (Scheme). Similary, Zn(II)-octa-(4-
chlorophenyl)- and Zn(II)-octa-(4-bromophenyl)
tetraazaporphyrin were obtained according to the methods
given in [14, 15]. We studied the effect of the para-halogena-
tion of the phenyl groups of the series of Zn(II)-
octaphenyltetraazaporphyrins derivatives on their fluores-
cence quantum yields and Stokes shifts. The experimental
data were supplemented by quantum-chemical calculations
* Nugzar Z. Mamardashvili
ngm@isc-ras.ru; https://orcid.org/0000-0001-9778-5227
Olga A. Dmitrieva
https://orcid.org/0000-0002-3251-7392
Natalya V. Chizhova
https://orcid.org/0000-0001-5387-5933
1
G. A. Krestov Institute of Solution Chemistry of the Russian
Academy of Sciences, Akademicheskaya Str. 1, Ivanovo, Russian
Federation 153045
2
Ivanovo State University of Chemistry and Technology,
Sheremetevskiy Av. 7, Ivanovo, Russian Federation 153000

J Fluoresc
performed by the method density functional theory (DFT) and
time-dependent DFT (TD-DFT) calculations. It was shown
that substituents in the phenyl rings of the macrocycle strongly
influence on the fluorescent properties and stability of π-
molecular orbitals of aromatic conjugated systems compared
to unsubstituted porphyrazine as the atomic number of the
attached halogen increases.
with water and dried. The filtrate was washed thoroughly with
water, a dilute sodium thiosulfate solution and again with wa-
ter. The precipitate formed after 2 days was filtered off and
1
dried. Yield: 1.2 g (0.004 mol), 40%. H NMR (CDCl3, δ,
ppm): 7.76 d (16Н, ortho-C6H5, J 7.70 Hz), 7.58 d (16Н,
meta-C6H5, J 7.60 Hz). Mass spectrum, m/z (Irel,%) 299.7
(88) [M]+ and was calculated for С16Н8Cl2N2–299.4.
Zn(II)-octa-(4-chlorophenyl)tetraazaporphyrin
(Cl8 OPhPaZn). The ground mixture of di-(4-
chlorophenyl)maleonitrile (0.1 g, 0.334 mmol) and ZnCl2
(0.046 g, 0.334 mmol) was heated in a test tube with a gas
vent tube in a stream of argon for 4 min at 260-2700С. The
product was cooled and dissolved in benzene,
chromatographed on alumina with dichloromethane, then
Experimental
Materials and Methods
Zinc chloride (Acros), solvents (“chemical pure” grade),
chloroacetonitrile, bromoacetonitrile (Acros), alumina
(Merck) were used without additional purification. UV-Vis
spectra were recorded on a Cary 100 (Varian) spectrophotom-
eter at room temperature. IR spectra were registered on a
1
chloroform. Yield: 0.043 g (0.0341 mmol), 41%. H NMR
(CDCl3, δ, ppm): 8.10 d (16Н, ortho-C6H5, J 7.70 Hz), 7.57
d (16Н, meta-C6H5, J 7.60 Hz). IR (ν, сm−1): 2924 s, 2850 m
ν(C-H, Ph), 1631 m ν(C=C, Ph), 1467 m, 1370 m ν(C=N),
1308 w ν(C-N), 1143 m, 1075 w 1065 w δ(C-H, Ph), 984 s
ν(C-Cl), 877 m, 825 m ν(С-С), 769 w, 746 w, 695 s γ(C-H,
pyrrole ring), 605 m γ(С-Н, Рh), 536 m ν(Zn-N). Mass spec-
trum, m/z (Irel,%) 1263.5 (97) [M + Н]+; calculated for
С64Н32Cl8N8Zn – 1262.1.
1
Vertex 80v Fourier spectrometer in KBr pellets. H NMR
spectra were recorded on a Bruker AV III-500 spectrometer
(internal standard was tetramethylsilane, TMS). Mass spectra
were obtained on a Maldi TOF Shimadzu Biotech Axima
Confidence mass spectrometer (matrix – dihydroxybenzoic
acid). Fluorimetric measurements of metalloporphyrins solu-
tions in toluene (Sigma-Aldrich) were carried out on a
Shimadzu RF-5301 fluorimeter according to the procedure
[16, 17].
Di-(4-bromophenyl)maleonitrile was synthesized accord-
ing to the procedure described in [28]. Zn(II)-оcta-(4-
bromophenyl)tetraazaporphyrin (Br8OPhPaZn). The ground
mixture of di-(4-bromophenyl)maleonitrile (0.1 g,
0.258 mmol) and ZnCl2 (0.035 g, 0.258 mmol) was heated
in a test tube with a gas vent tube in a stream of argon for
5 min at 265-2750С. Further isolation and purification of the
product is similar to the Cl8OPhPaZn. Yield: 0.039 g
Theoretical Calculations
Structures of halogenated series of Zn(II)-octapheny
ltetraazaporphyrins were performed on the base of DFT with
the BP86 functional [18, 19] and def2-TZVP basis set [20].
The BP86 functional was chosen here since it is known that it
provide highly accurate geometries for tetrapyrrolic
macrocycles [21–24]. Vibration frequencies are used to char-
acterize the optimized structures where the energy is minima
without imaginary frequencies. Excitation energies were com-
puted using TD-DFT methods with the same functional and
basis set. All quantum chemical calculations were performed
in toluene using the GAMESS v.12 software package [25].
The polarizable continuum model (PCM) [26, 27] allowed
evaluating solvation effects.
1
(0.0241 mmol) (37%). H NMR (CDCl3, δ, ppm): 8.01 d
(16Н, ortho-C6H5, J 7.70 Hz), 7.77 d (16Н, meta-C6H5,
J
7.60 Hz). IR (ν, сm−1): 2925 m, 2852 a ν(C-H, Ph), 1622 m
ν(C=C, Ph), 1474 m, 1366 w ν(C=N), 1304 w ν(C-N),
1139 m, 1072 m, 1060 m δ(C-H, Ph), 980 s ν(C-Br), 873 w,
833 m ν(С-С), 770 w, 744 w, 697 m γ(C-H, pyrrole ring),
615 m γ(С-Н, Рh), 522 m ν(Zn-N). Mass spectrum, m/z
(Irel,%) 1618.7 (86) [M + Н]+; calculated for С64Н32Br8N8Zn
– 1617.7.
Results and Discussion
Synthesis
Synthesis and Characterization
Di-(4-chlorophenyl)maleonitrile. 2.6 ml (3.05 g, 0.02 mol) of
chloroacetonitrile was added to the mixture of iodine (15.5 g,
0.06 mol) in 15 ml of methanol and diethyl ether (130 ml),
cooled with ice. A cold solution of sodium methylate prepared
from sodium (0.95 g, 0.13 mol) and methanol (15 ml) was
added to the reaction mixture with stirring for 30 min. The
yellowish precipitate was filtered off after 50 min, washed
It is shown that template cyclotetramerisation of chloro-
substituted diphenylmaleonitrile with zinc(II) chloride
(1:1 M ratio of reagents) at 260-2700С for 4 min led to the
formation of Zn(II) octa-(4-chlorophenyl)tetraazaporphyrin.
Similarly, Zn(II) octa-(4-bromophe-nyl)tetraazaporphyrin
was obtained by fusing di-(4-bromophenyl)maleonitrile with
zinc(II) chloride (1:1 M ratio) at 265-2750С for 5 min

J Fluoresc
1H NMR spectrum of the chloro-substituted compound
Cl8OPhPaZn in CDCl3 contains signals of ortho- and meta-
protons at 8.10 and 7.57 ppm. The signals of ortho- and meta-
protons of Br8OPhPaZn are at 8.01 and 7.77 ppm
(experimental)
IR spectra of Cl8OPhPaZn and Br8OPhPaZn in KBr tablets
are shown in Fig. S3-S5. A significant change of the bands
intensity in the 2900 cm−1 region is observed in the IR spec-
trum of bromo-substituted Zn porphyrazine (Fig. S4) com-
pared with chloro-substituted Zn porphyrazine (Fig. S3).
Ground-State Geometry
The optimized structures of series of halogenated Zn(II)-
octaphenyltetraazaporphyrins with the selected bond lengths
and angles with the indicated atom numbering are shown in
Fig. 2. The results of the calculated geometric parameters of
Cl8OPhPaZn and Br8OPhPaZn showed that halogenation of
the para-position of the phenyl groups of macrocycle leads to
an increase of C1-C2 and C2-C2 bonds lengths of the pyrrole
groups by ca. 0.1 Å in comparison to the unsubstituted com-
pound (Fig. 2).
The length of these bonds aligns and the dihedral angle
formed by the C1-C2-C3-C4 carbon atoms slightly rises with
increasing of halogen atomic number and amounts to ~ 44°
(Fig. 2). An increase of the rotation angle of the phenyl ring
plane relative to the macrocycle plane leads to a weakening of
the π-conjugation between the porphyrazine pyrrole rings and
aryl fragment [30].
Fig. 1 UV-Vis spectra of Cl8OPhPaZn and Br8OPhPaZn in chloroform
(Scheme). The UV-Vis spectra of synthesized compounds in
chloroform are shown in Fig. 1 Scheme 1.
The characteristics of the UV-Vis spectra of chloro- and
bromo-substituted Zn(II)-porphyrazines in comparison with
the previously obtained fluoro-substituted (F8OPhPAZn)
[15] and unsubstituted Zn(II)-octaphenyltetraazaporphyrin
(OPhPaZn) [29] are given in Table 1.
It is known that meso-azasubstitution of the tetrapyrrolic
macrocycle leads to a blue shift of the Soret band in compar-
ison with the porphyrins. There is one intense Q-band (I) and
vibrational satellite (II-band) in the UV-Vis spectra of Zn(II)-
octaphenyltetraazaporphyrins. The red shift of the absorption
bands is observed in going from an unsubstituted Zn-
porphyrin to the halogen-substituted compound with a larger
atomic mass.
Energy Gap
The signals with a value of m/z 1263.5 and 1618.7 haloge-
nated Zn-porphyrins are fixed in the mass spectra correspond-
ing to the molecular ions of Cl8OPhPaZn and Br8OPhPaZn
(Fig. S1-S2, experimental).
An analysis of the distribution of molecular orbital energies in
the neighborhood of highest occupied molecular orbitals
(HOMO and HOMO-1) and lowest unoccupied molecular
orbitals (LUMO and LUMO+1) as well as the width of the
Scheme 1 Please see manu

J Fluoresc
Table 1 UV-Vis-spectra of Zn(II)
octaphenyltetraazaporphyrins in
DMF
Compound
Band I λ, nm, lg(ε)
Band II λ, nm, lg(ε)
Soret band λ, nm, lg(ε)
Reference
[15]
F8OPhPaZn
Cl8OPhPaZn
Br8OPhPaZn
OPhPaZn*
OPhPaZn
635 (5.02)
639 (4.97)
641 (4.98)
636 (4.84)
636 (4.91)
582sh. (4.47)
583sh. (4.32)
586sh. (4.46)
583sh. (4.35)
583 sh. (4.33)
382 (4.91)
385 (4.84)
385 (4.89)
379 (4.76)
380 (4.83)
[29]
*in DMSO
energy gaps HOMO-LUMO (EH-L) for Cl8OPhPaZn and
Br8OPhPaZn were performed. The electron density distribu-
tion of HOMO, HOMO-1, LUMO and LUMO+1 was obtain-
ed using TD-DFT BP86 (PCM)/def2-TZVP level (Fig. 3).
Quantum-chemical calculations showed that the presence of
the halogen on the para-position of the phenyl groups leads to
stabilization of the π-molecular orbitals of aromatic conjugat-
ed systems compared to unsubstituted OPhPaZn as the atomic
number of the attached halogen increases, which is consistent
with published data [31–33]. However, the presence of the
halogen atom in phenyl rings affects LUMO energy more than
the HOMO, which leads to a decrease in the energy gap
(HOMO-LUMO) from 1.646 to 1.625 eV in the series
OPhPaZn > F8OPhPaZn > Cl8OPhPaZn > Br8OPhPaZn (Fig.
3). In going from an unsubstituted Zn-porphyrin to halogen-
substituted compound with a higher atomic mass, the increase
of the stability of LUMO compared to HOMO is observed,
which leads to a shift of the Q-band to the long-wavelength
region. The results obtained are confirmed by experimental
data (Fig. 3, Table 1).
Molecular orbitals visualization is also helpful for descrip-
tive understanding on their excitation types. The molecular
orbitals involved in the excitation are displayed in Fig. 3.
The calculated orbital models show that π–π* nature of the
Fig. 2 Front and side views of the
calculated structures and selected
geometrical parameters for the
halogenated Zn(II)-
octaphenyltetraazaporphyrins
optimized at the BP86 (PCM)/
def2-TZVP level in toluene

J Fluoresc
Fig. 3 The molecular orbitals
energy of halogenated Zn(II)-
octaphenyltetraazaporphyrins
calculated by the TD-DFT meth-
od with BP86/def2-TZVP. TD
calculations were performed in
toluene using the PCM solvation
model
transition among HOMO, HOMO-1, LUMO and LUMO+1 is
observed only for OPhPaZn. This follows from the localiza-
tion of electrons on the π-orbitals of the macrocycle central
rings. In the case of halogenated porphyrazines, phenyl π-
orbitals have a greater contribution to HOMO and HOMO-1
compared to unsubstituted OPhPaZn, while their LUMO and
LUMO+1 do not contain a noticeable electron density distri-
bution on the phenyl rings of studied macrocycles. This sug-
gests that the HOMO → LUMO and HOMO-1 → LUMO+1
transitions are mixed character of transfers, including π–π *
transfers and charge transfer. The direction of charge transfer
diverges from phenyl rings to the center of the macrocycle.
identical conditions, including absorption at the excitation
wavelength, reflecting the relative fluorescence emission
quantum yields of Zn porphyrins. The following equation
was used to determine the quantum yields (ФFl) [16]:
IxAstn2x
ΦFl ¼ Q
st IstAxn2st
where Qst is the fluorescence quantum yield of the Zn-
phthalocyanine standard (0.3 in pyridine [34]), Ax and Ast
are the absorbance values of the sample and standard at the
excitation wavelength respectively, Ix and Ist are integrated
intensities of the sample and standard respectively, nx and nst
are the refractive indices of solvents in which the sample and
standard were dissolved. The calculated fluorescence quan-
tum yields (ФFl) are presented in Table 2. The error of fluori-
metric measurements was ~ 10%.
Fluorescence Emission Spectroscopy
The fluorescence emission spectra of halogenated Zn-
porphyrins at 25 °C in toluene are shown in Fig. 4. The emis-
sion spectra of studied compounds were recorded under

J Fluoresc
and stronger polarization in the excited state. The nature
of the halogen atom affects energy stability and quantum
yield (Table 2). So, decrease of EH-L is observed in the
series OPhPaZn>F8 OPhPaZn > Cl8 OPhPaZn >
Br8OPhPaZn (Fig.4), which are in good agreement with
the experimentally revealed trends in the quantum yield of
fluorescence (Table 2).
60
50
40
30
20
10
0
OPhPaZn
F OPhPaZn
8
Cl OPhPaZn
8
Br OPhPaZn
8
Conclusions
Thus, Zn(II) complexes of the octa(4-chlorophenyl)- and
octa(4-bromophenyl)-tetraazaporphyrins were synthesized
and identified. The geometry was optimized for the com-
pounds and studied by the density functional method and the
energy distribution of the molecular orbital higher occupied
molecular orbital and the lower free orbital and the energy gap
widths HOMO – LUMO (EH-L) were analyzed. Fluorimetric
m e a s u r e m e n t s o f h a l o g e n a t e d Z n ( I I ) -
octaphenyltetraazaporphyrins solutions were completed and
a comparative analysis of the fluorescence quantum yields of
the compounds studied was carried out. Quantum-chemical
calculations showed that HOMO-LUMO transition make ma-
jor contribution to the fluorescence of studied
tetraazaporphyrins. Excitation of the halogenated OPhPaZn
leads to redistribution of electron density and stronger polar-
ization in the excited state. Taking into account the fact that
substitution with halogens (F−, Cl−, Br−) at meso-phenyl po-
sition influence on the electronic density distribution within
the core of the macrocycle, and thus determine its fluores-
cence properties, the results obtained could be used in the
design of new porphyrin based materials with nonlinear opti-
cal properties, catalytic and biomedical activity.
600
620
640
660
680
700
720
740
,nm
Fig. 4 Fluorescence spectra of the Zn(II) octaphenyltetraazaporphyrins in
toluene at λex = 375 nm
The obtained results showed that the presence of the halo-
gen on the para-position of the phenyl groups significantly
affects the magnitude of obtained quantum yields of fluores-
cence emission but does not significantly affects the Stokes
shifts (ΔSS). The data in Table 2 show only modest Stokes
shifts in the range 276.87 ÷ 296.98 cm−1, which indicates a
slight relaxation of the molecule geometry occurring in the
first excited state of studied compounds, and also illustrates
the low sensitivity of studied compounds to the halogen na-
ture. Para-halogenation of the phenyl fragments of the
macrocycle quenches the fluorescence emission of OPhPaZn
progressively as the atomic number of the attached halogen
increases. The downward trend in fluorescence emission and,
consequently, in quantum yield is due to the heavy atom ef-
fect, which induces a spin-orbit interaction and contributes to
the intersystem transition to the triplet state [35]. Thus, the
presence of a heavy atom in the para-position of the phenyl
fragments quenches the excited singlet state in the following
sequence: OPhPaZn> F8OPhPaZn > Cl8OPhPaZn >
Br8OPhPaZn (Table 2).
Acknowledgements This work was supported by the Russian Science
Foundation (project number 19-73-200-79) and employed with the equip-
ment of the Shared Facilities Center of the Institute of Organic Chemistry
of the Russian Academy of Sciences.
The authors thank the Joint Supercomputer Center of the Russian
Academy of Sciences (Moscow) for providing the resources of the
MVS-100 K cluster.
Quantum-chemical calculations showed that HOMO-
LUMO transition make major contribution to the fluores-
cence of studied Zn-porphyrins. Excitation of the haloge-
nated OPhPaZn leads to redistribution of electron density
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