A New Sensitive and Selective Off-On Fluorescent Zn2+ Chemosensor Based on 3,3′,5,5′-Tetraphenylsubstituted Dipyrromethene

Article abstract of DOI:10.1007/s10895-016-1890-4

3,3′,5,5′-Tetraphenyl-2,2′-dipyrromethene was described as a highly sensitive and selective Off-on fluorescent colorimetric chemosensor for Zn²⁺ based on the chelation-enhanced fluorescence (CHEF) effect. The reaction of dipyrromethene ligand with Zn²⁺ induces the formation of the [ZnL₂] complex, which exhibits the increasing fluorescence in 120 fold compared with ligand in the propanol-1/cyclohexane (1:30) binary mixture. The Zn²⁺ detection limit was 1.4?×?10^?7 М. The UV-Vis and fluorescence spectroscopic studies demonstrated that the dipyrromethene sensor was highly selective toward Zn²⁺ cations over other metal ions (Na⁺, Mg²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Cd²⁺ and Pb²⁺), excluding Hg²⁺.

Full text of DOI:10.1007/s10895-016-1890-4

J Fluoresc
DOI 10.1007/s10895-016-1890-4
A New Sensitive and Selective Off-On Fluorescent
Zn2+ Chemosensor Based on 3,3′,5,5′-Tetraphenylsubstituted
Dipyrromethene
Natalia A. Bumagina1 & Elena V. Antina1 & Anna Yu. Nikonova2 & Mikhail B. Berezin1
Alexander A. Ksenofontov1 & Anatoly I. Vyugin1
&
Received: 23 May 2016 /Accepted: 19 July 2016
#
Springer Science+Business Media New York 2016
. .
Keywords Dipyrromethene Fluorescentchemosensor Zinc
Abstract 3,3′,5,5′-Tetraphenyl-2,2′-dipyrromethene was de-
scribed as a highly sensitive and selective Off-on fluorescent
colorimetric chemosensor for Zn2+ based on the chelation-
enhanced fluorescence (CHEF) effect. The reaction of
dipyrromethene ligand with Zn2+ induces the formation of the
[ZnL2] complex, which exhibits the increasing fluorescence in
120 fold compared with ligand in the propanol-1/cyclohexane
(1:30) binary mixture. The Zn2+ detection limit was 1.4 × 10−7
М. The UV-Vis and fluorescence spectroscopic studies demon-
strated that the dipyrromethene sensor was highly selective
toward Zn2+ cations over other metal ions (Na+, Mg2+, Co2+,
Ni2+, Fe3+, Cu2+, Mn2+, Cd2+ and Pb2+), excluding Hg2+.
.
.
ion Selectivity Theoretical calculation
Introduction
Increasing sensitivity and availability of the detection methods
of biologically important and toxic metal ions is one of the most
important goals of research in the sensorics field. To achieve this
purpose, various methods such as mass spectrometry, atomic
absorption spectroscopy, high performance liquid chromatogra-
phy were developed. At the same time, these methods include
laborious procedures and requires of the using complex equip-
ment. Among the numerous physical and chemical methods of
analysis, the electron spectroscopy methods have a special
place, of which the fluorescence method is the most sensitive.
The fluorescence is a powerful tool due to its simplicity, easy
implementation, high sensitivity and detection limit of the ana-
lyte. When adding fluorescent chemosensor to a solution of
metal ion due to the reaction between them, a color change,
which can be observed with the naked eye under visible light
or under a UV lamp, and changes of the absorption and fluores-
cence characteristics are occurred.
* Natalia A. Bumagina
nad@isc-ras.ru
Elena V. Antina
eva@isc-ras.ru
Anna Yu. Nikonova
aynikonova@mail.ru
Mikhail B. Berezin
mbb@isc-ras.ru
Fundamental principles of chemosensorics and compre-
hensive understanding about fluorescent chemosensors were
reflected in a series of major reviews, including [1–6]. A large
number of organic compounds of different structures such as
rhodamines, quinolines, pyridine derivatives, oligopyrroles,
et al. were tested as fluorescent chemosensors [7–10].
Interaction of fluorescent chemosensor with detectable cat-
ion leads to the formation of the complex and is accompanied
by a fluorescence buildup or quenching fluorescence. Thus,
On-off and Off-on chemosensors are distinguished, respec-
tively. Off-on chemosensors are a greatest interest.
Alexander A. Ksenofontov
ivalex.09@mail.ru
Anatoly I. Vyugin
aiv@isc-ras.rus
1
G. A. Krestov Institute of Solution Chemistry of Russian academy of
Sciences 1 Akademicheskaya St., Ivanovo, Russian Federation
153045
2
Inorganic Chemistry Department, Ivanovo State University of
Chemistry and Technology, 7 Sheremetevskij prosp,
Ivanovo, Russian Federation 153000

J Fluoresc
Receptors in organic cation chemosensors can contain dif-
ferent functional groups, which are based on electron donor
heteroatoms (nitrogen, oxygen, etc.).
Cation chemosensors with receptors based on the oxygen
donor atoms exhibit the sensory properties predominantly to-
wards of alkali, alkaline earth and rare earth ions. For exam-
ple, fluorescence of chemosensors with crown ether substitu-
ents is effectively enhanced when coordination to potassium
and magnesium cations [11–13]. Fluorescent chemosensors
based on the nitrogen-containing heterocycles are widely used
for the detection of the transition metal ions [7, 14, 15].
Despite the large arsenal of known chemosensors, an active
search of new analytic agents with higher sensitivity, selectiv-
ity and detection limit of cation does not stop at the present
time.
Over the past 10 years the acyclic oligopyrroles and their
derivatives generated considerable interest. The hybrid mole-
cules of chelating ligands, covalently bounded to BF2-
dipyrromethenes (BODIPY), have gained recognition due to
the wide range of applications as fluorescent sensors of cations
[16–19]. However, the synthesis of these hybrid molecules is
very laborious. On the other hand, dipyrromethene ligands
also possess useful properties, including strong absorption in
the visible region of the spectrum and fluorescence buildup by
the coordination with Zn(II), Al(III), Si(IV), Sn(IV) and some
others cations [20–26].
N
NH
Fig. 1 Structure of 3,3′,5,5′-tetraphenyl-2,2′-dipyrromethene (HL)
Experimental
Reagents and Chemicals
The analysis of HL activity as fluorescent chemosensor towards
Zn2+ cations and the influence of other cations (Na+, Mg2+,
Mn2+, Co2+, Ni2+, Fe3+, Cu2+, Cd2+, Hg2+, Pb2+) was carried
out in the propanol-1/cyclohexane (1:30) binary mixture.
Propanol-1 (UVIR-HPLC-HPLC preparative, PAI) and cy-
clohexane (Panreac, Barcelona) were used without further
purification.
The 1,7-dibromine-2,6-dimethyl-3,5-diamyl-BODIPY in
ethanol with fluorescence quantum yield 0.30 [34] was used
as a standard for the determination of fluorescence quantum
yield of HL.
Reaction of dipyrromethenes with zinc ions gives the
largest fluorescent response compared to the other above
listed cations. For example, upon detection of zinc cations
using the meso-aryl dipyrromethenes, the fluorescent re-
sponse reaches 72 [27]. Detection of zinc cations is par-
ticular interest because Zn2+ ions play an important role in
many biological processes. However, studies of
chemosensory activity of dipyrromethene ligands is ex-
tremely limited [27–32].
Synthesis
of the 3,3′,5,5′-Tetraphenyl-2,2′-Dipyrromethene
The 3,3′,5,5′-tetraphenyl-2,2′-dipyrromethene was prepared
using procedure described in [35, 36].
A mixture of 0.44 g (2.02 mmol) of 3,5-diphenylpyrrole,
0.5 g (2.02 mmol) of 2-formyl-3,5-diphenylpyrrole, 10 ml of
acetic acid, and 2.5 ml of acetic anhydride was heated at reflux
We have previously shown [33] that 3,3′,5,5′-
tetraphenyl-2,2′-dipyrromethene (HL) with the Zn(II)
forms homoligand complex of composition [ZnL2].
Ligand HL is very weak fluorophore with fluorescence
quantum yield (φ) less than 1·10−3. The [ZnL2] complex
gives intense fluorescence with a maximum in the region
from 608 to 615 nm depending on the solvent properties.
Moreover, the fluorescence quantum yield of [ZnL2]
reaches 33 % in non-polar environments (cyclohexane,
hexane, benzene, toluene) and is reduced with increasing
solvent polarity (chloroform, alcohols, DMF). These pre-
suppositions provide a basis for the study of HL as a new
chemosensor for the zinc cations and selection of the me-
dium optimal conditions for its maximum sensory activity.
In this paper the first results of a study of sensitivity and
selectivity of the new fluorescent chemosensor of zinc cations
on the basis of 3,3′,5,5′-tetraphenyl-2,2′-dipyrromethene HL
(Fig. 1) were presented.
[ZnL2]
0,08
529 nm
+Zn2+
0,04
HL
0
250
350
450
550
650
Wavelength, nm
Fig. 2 UV − Vis spectral changes during a titration of HL
(1.3 × 10−6 mol L−1) by the 2–34-fold molar excess of Zn(AcO)2 in
propanol-1/cyclohexane (1:30) binary mixure

J Fluoresc
for 1 h. The solution became crimson and a precipitate
formed. The resultant precipitate was separated by filtration,
washed with methanol, and dried. The acetic acid solution was
poured into 200 ml of water. The precipitate was separated by
filtration, dried, and chromatographed on silica gel (L 100/
250, chloroform as an eluent). Yield is 0.7 g (77.2 %).
and fluorescence spectra before and after addition of a
zinc salt or mixture of several metal salts was performed.
Fluorescent response I609=Io594 was calculated as the ratio
of the fluorescence intensity in the spectra after addition
of the zinc acetate (I609) to the fluorescence intensity in
spectrum of the sensor (Io594 ).
Electronic Absorption Spectrum: λmax at 532; 295 nm
(Benzene)
Theoretical Calculations
All calculations were carried out using the PC GAMESS v.12
program package [37]. The geometries of all compounds were
optimized by density functional calculations employing the
hybrid B3LYP function and a mixed basis set, i.e., the 6-
31G(d,p) basis set for non-metallic atoms and the Los
Alamos effective core potential basis set (LANL2DZ) for zinc
atom [38–40]. Frequency analyses were then performed to
confirm that the optimized geometries are true minima on
the potential energy surface. Subsequent single-point calcula-
tions were performed with the same method and basis sets but
in a cyclohexane solvent environment represented by the po-
larizable continuum model.
1H NMR (δ, ppm): 14.35 (br s, 1H, NH), 7.94–8.03 (m, 8H, o-
H-Ph), 7.42–7.60 (m, 12H, m,p-H-Ph), 6.99 (s, 2H, 4,4′-H),
6.76 (s, 1H, ms-H).
For C33H24N2 anal. Calcd. (%): C, 88.36; H, 5.39; N, 6.25.
Found (%): C, 88.51; H, 5.18; N, 6.12.
Mass spectrum MALDI-TOF: calculated (C33H24N2)
m/z = 448.57, found m/z = 449.04.
Apparatus
UV/Vis and fluorescence (at λex = 505 nm) spectra in
the visible 250–700 and 350–750 nm range respectively
were recorded on SM2203 (SOLAR) spectrofluorimeter.
1H NMR (500 MHz) spectra of the dipyrromethene in
CDCl3, using TMS signal as an internal reference, were mea-
sured by a Avance-500 spectrometer (Bruker, Germany) in the
BThe upper Volga region centre of physico-chemical
research^ of G.A. Krestov Institute of Solution Chemistry of
Russian academy of sciences.
Element analysis (C, H, N) of the dipyrromethene was
performed on analyzer Flesh EA1112 (TermoQuest, Italy).
Mass spectrum (MALDI-TOF) of dipyrromethene HL
was performed on AXIMA Confidence (Shimadzu)
MALDI-TOF mass spectrometer.
Results and Discussion
Spectrophotometric Detection of Zn2+
Electronic absorption spectrum (UV-Vis) of the molecular
form of sensor HL in cyclohexane is characterized by band
with a maximum at 526 nm (ε = 31,568 L·mol−1·cm−1). To
investigate the binding ability of HL toward Zn2+, UV/Vis
spectra of HL (1.3 × 10−6 mol L−1) in the presence of various
concentrations of Zn2+ (0–4.4) × 10−5 mol L−1 in the 1-
propanol/cyclohexane (1:30) binary mixture were recorded.
This binary mixture of solvents was selected according to data
on the highest fluorescent response of reaction and satisfacto-
ry solubility of reagents and the resulting helicates [41].
Observed in Fig. 2 changes in the electronic absorption
spectra appear in a result of coordination of HL by the Zn2+
with the formation of homoligand [ZnL2] complex (Fig. 3),
the structure of which was confirmed previously [33].
General UV–Vis and Fluorescence Spectra Measurements
The spectrophotometric titration was performed using the
method of molar ratios. The molar series of solutions
with constant concentration of ligand (HL) and varying
concentration of the zinc acetate cZn2þ =cHL from 0 to 34
were prepared by adding Zn(II) acetate solution to the
HL solution (1.3 × 10−6 mol L−1) in propanol-1/cyclo-
hexane binary mixture. Registration of the absorption
As seen in Fig. 2, during the titration of ligand solution by
the Zn2+ acetate solution in the electronic absorption spectra
Ph
Ph
Fig. 3 Formation of the complex
Zn(II) with dipyrromethene HL,
and images of sensor in the
Ph
Ph
N
N
N
N
Zn2+
absence (left) and presence (right)
of 10-fold excess of Zn2+ under
Ph
Ph
Ph
Ph
Zn
the visible and UV (λex = 366 nm)
light
N
NH
Ph
Ph
Vis UV
Vis UV
Ph
Ph

J Fluoresc
of 550–558 nm is registered, and the quantum yield is signif-
icantly increased (φ = 15 %) (Fig. 4).
1,2
0,8
0,4
0,0
λ
λ
ex = 366 nm
Taking into account this feature, the chemosensory ability
of dipyrromethene was evaluated with excitation at 505 nm,
that allowed increasing dipyrromethene fluorescent response
in analytical reaction with zinc ions. Titration of
dipyrromethene HL solution (cHL= 1.3 × 10−6 mol L−1) by
the zinc acetate solution was carried out before the molar ratio
cZn2þ =cHL = 34. As shown in Fig. 5, during titration the red
shift of the emission band maximum (λmax from 594 to
609 nm) and the growth of fluorescence intensity were ob-
served. In this case, the color change of the solution from
yellow-green to bright orange can be seen by the naked eye.
The fluorescence intensity reaches a maximum value at a
molar ratio cZn2þ =cHL = 10 (Fig. 5, insert). Further increasing
zinc acetate(II) concentration (cZn2þ =cHL = 10–34) does not
cause noticeable changes in fluorescence intensity (Fig. 5,
insert). The maximum fluorescent response of reaction was
120. The fluorescence buildup of the dipyrromethene chromo-
phore in the complex with Zn2+ can be attributed to the highly
efficient chelation-enhanced fluorescence effect (CHEF-ef-
fect), associated with an increased rigidity of the sensor mol-
ecules due to chelation.
max = 550-558 nm
λ
λ
ex = 505 nm
max = 594 nm
450 500 550 600 650 700
Wavelength, nm
Fig. 4 Fluorescence spectra of 3,3′,5,5′-tetraphenyl-2,2′-dipyrromethene
HL in the propanol-1/cyclohexane (1:30) binary mixure at excitation on
366 and 505 nm
the HL band with a maximum at 526 nm is transformed into a
more intense band of complex with λmax at 529 nm.
Fluorescent Detection of Zn2+
The studied previously free dipyrromethenes exhibit very
weak fluorescence independently of the wavelength of the
exciting light, composition and properties of the medium
[29]. We have found that the fluorescence of 3,3′,5,5′-
tetraphenyl-2,2′-dipyrromethene depends on the wavelength
of the exciting light. Thus, the HL in 1-propanol/cyclohexane
(1:30) binary mixture upon excitation by visible light
(λex = 505 nm) gave a very weak fluorescence with low in-
tense band at λmax = 594 nm (Fig. 4) and quantum yield of less
than 0.001. Upon excitation of HL by UV light with λex from
300 to 400 nm in the same binary solvent, in the fluorescence
spectrum more intense broadened band with λmax in the range
Theoretical Calculations
For theoretical justification the reasons of fluorescence en-
hancement of [ZnL2] complex in comparison with HL the
orbital energy analysis (ЕHOMO, ЕLUMO) and the width of
the HOMO–LUMO energy gaps (Еg) analysis was carried
out. The electron density distribution of HOMO and LUMO
orbitals obtained by the PCM(cyclohexane)/B3LYP/6-
I609 / I5o94
120
Fig. 5 Fluorescence emission
spectral changes during a titration
of the HL (1.3 × 10−6 mol L−1
)
with Zn(AcO)2 in the propanol-1/
cyclohexane (1:30) at λex fixed at
505 nm. Insert: Fluorescence
spectrum of dipyrromethene HL,
fluorescence intensity changes (at
609 nm) as a function of molar
ratiocZn2þ =cHL and images of
sensor in the absence and
90
[ZnL2]
8
6
4
2
0
60
30
0
+ Zn2+
0
10
20
30
cZn2 /cHL
HL HL+Zn2+
+
2+
presence of 10-fold excess of
Zn2+ under the UV light
Ifl
0,1
(λex = 366 nm)
0,05
0
580
600
620
λ, nm
550
600
650
700
Wavelength, nm

J Fluoresc
Fig. 6 The distribution of
boundary molecular orbitals of
HL and [ZnL2] and the energy
gap values (Eg = ЕHOMO, ЕLUMO),
(PCM(cyclohexane)/B3LYP/6-
31G(d,p) + LANL2DZ)
31G(d,p) + LANL2DZ and shown in Fig. 6. The quantum–
chemical calculations showed that HOMO–LUMO transition
makes major contribution to the fluorescence of the studied
compounds. Figure 6 demonstrate the distribution of the elec-
tron density of molecular HOMO and LUMO orbitals in the
HL and [ZnL2] molecules.
Quantum-chemical calculations showed that complexing
influences on the spectral-luminescent properties. At the tran-
sition from of the ligand HL to the corresponding Zn complex
incremented the energy gap value (on 0.07 eV) (Fig. 6). The
observed pattern in good agreement with experimentally ob-
servable trends of change of fluorescence of the
dipyrromethene HL and the resulting Zn complex in during
titration (fluorescent Boff-on^ response).
1.4 × 10−7 mol L−1, i.e. the sensor in sensitivity is not inferior
by many the best analytical agents on zinc ions [43, 44].
Selectivity
Selectivity of detecting analyte is another important indicator
of sensor. Figure 8 shows the differences in the color of HL
solutions with 10-fold excess of different metal cations in the
1-propanol/cyclohexane (1:30) binary mixture when excited
by UV light (λex = 366 nm). Change of solution color from
yellow-green to bright orange was visible to the naked eye
only with addition of zinc ions. In the presence of other ions
Detection Limit
The detection limit is one of the important indicators of analite
sensitivity determination. For many practical purposes, includ-
ing for biochemical studies, important to determine very low
concentrations of cations. As a result of fluorescence measure-
ments during titration of ligand solution by the zinc(II) acetate
solution, the dependence of Log [(I–Io)/(Imax–I)] as function of
Log [Zn2+] was obtained (Fig. 7) by analogy [42]. The detec-
tion limit of Zn2+ ions, using the ligand HL, was
Log [Zn2+]
Fig. 7 Relative fluorescence intensity as a function of the logarithm of
Zn2+ concentration

J Fluoresc
Fig. 8 The color of HL solutions
with 10-fold excess of the cations
of different metals in the 1-
propanol/cyclohexane (1:30) bi-
nary mixture when excited by UV
light (λex = 366 nm)
HL
Zn2+
Na+
Mg2+ Mn2+ Co2+
Ni2+
Cu2+ Cd2+ Hg2+ Pb2+
the solution color practically unchanged, because the com-
plexation with alkali (Na+), alkaline earth (Mg2+) and some
d-metals (Mn2+, Co2+, Ni2+ and Cd2+) does not occured, or
non-fluorescent complexes with Cu2+, Pb2+ are formed.
As can be seen from Fig. 9a, the dipyrromethene sensor HL
gives maximum fluorescent response (I609=Io594 = 120) in the
presence of Zn2+ cations. Also, Hg2+ ion enhances the fluo-
rescence intensity of HL, but the effect was weaker compared
with that of Zn2+ ion under similar concentration (Fig. 9a).
Addition of 10-fold excess of individual Mn2+, Co2+, Ni2+,
Fe3+, Cd2+, Pb2+ ions or 10 and 100-fold excess of Na+ and
Mg2+ to the sensor solution does not practically effect on the
sensor fluorescence (Figs. 8 and 9a). The sensor fluorescence
is completely quenched in the presence of Cu2+ cations, due to
their paramagnetic nature and electron or energy transfer be-
tween the metal cations and the ligand [17, 45–47].
It is known that the presence of other metal cations, particu-
larly Cu2+ [17, 46, 47], can negatively affect the Zn2+ ions deter-
mination. Therefore, to further evaluate the HL selectivity for
Zn2+, the dipyrromethene fluorescence spectra in the presence
of Zn2+ mixed with various metal ions (Na+, Mg2+, Mn2+,
Co2+, Ni2+, Fe3+, Cu2+, Cd2+, Hg2+ or Pb2+) in the propanol-1/
cyclohexane (1:30) binary mixure were recorded. Each of the
cations was taken in a tenfold molar excess, or in 10 or 100-
fold molar excess in the case of Na+ and Mg2+ ions relative to
HL content. The Na+, Mg2+, Mn2+, Ni2+, Fe3+, Cd2+ or Pb2+ ions
did’t interfere fluorescent detection of Zn2+ cations (Fig. 9b). If in
the solution the Zn2+/Co2+ or Zn2+/Cu2+ cation mixtures are pre-
sented, the fluorescence intensity of sensor is significantly (3 and
4 times, respectively) decreased (Fig. 9b) compared with the
sensor solution containing only Zn2+ ions. At the same time,
the maximum position of the fluorescence band of formed
[ZnL2] complex remains unchanged. Nevertheless, 3,3′,5,5′-
tetraphenyl-2,2′-dipyrromethene sensor can also be successfully
used for the Zn2+ detection in the presence of Co2+ and Cu2+ ions.
The fluorescence of HL/Zn2+ system was significantly quenched
(approximately 7 times) by Hg2+ that may be due
transmetallation to form a more stable and weakly fluorescing
complex of mercury with a fluorescence band maximum at
573 nm (Fig. 9a, b).
Conclusions
In summary, we developed fluorescent colorimetric
chemosensor based on the 3,3′,5,5′-tetraphenyl-2,2′-
a
b
I609 / I5o94
8
7
6
5
4
3
2
1
0
Zn2+
HL, Na+, Mg2+, Co2+,
Ni2+, Cu2+, Mn2+,
Pb2+, Cd2+, Fe3+
Hg2+
HL Zn2+ Na+ Mg2+ Cd2+ Ni2+ Mn2+ Fe3+ Pb2+ Co2+ Cu2+ Hg2+
550
600
650
700
Wavelength, nm
Fig. 9 Selectivity of HL (1.3 × 10−6 mol L−1) towards Zn2+ ions in
propanol-1/cyclohexane (1:30) upon excitation at 505 nm: (a) emission
spectra of HL in the presence of 10-fold excess of various metal ions
(Na+, Mg2+, Mn2+, Co2+, Ni2+, Fe3+, Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+);
(b) graph with gray bars representing the addition to sensor solution of
10-fold excess of various metal ions and striped bars representing the
addition to sensor solution of 10-fold excess of Zn2+ mixed with 10-
fold excess of the indicated metal ions

J Fluoresc
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