NJC

View Article Online

PAPER View Journal | View Issue

N-Arylated bisferrocene pyrazole for the

dual-mode detection of hydrogen peroxide:
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

Cite this: New J. Chem., 2019,

43, 8539 an AIE-active fluorescent ‘‘turn ON/OFF’’
and electrochemical non-enzymatic sensor†
Ezhumalai David, Thamodharan Viswanathan, Selvam Prabu and
Nallasamy Palanisami *

A series of new N-arylated bisferrocene pyrazole (D–p–A–p–D) chromophores have been synthesized
by the Chan–Lam cross-coupling (1, 2) and Buchwald–Hartwig amination (3, 4) reactions. The com-
pounds 1–4 were characterized using analytical and spectroscopic methods. Compounds 1 and 3
showed positive solvatochromism and later, compounds 2 and 4 exhibited negative solvatochromism.
The compounds 1–4 interestingly exhibited highly enhanced fluorescence intensity in their aggregate
states, while in the solution states, they exhibited low fluorescence intensity. The origin of enhanced
Received 20th March 2019, emission in the aggregated state was due to the restriction of intramolecular rotation, especially in the
Accepted 2nd May 2019 mixture having a ratio of 40 : 60 (CH3CN/H2O). The aggregation-induced emission (AIE) properties were
DOI: 10.1039/c9nj01471c utilized to detect H2O2, which showed a quick response in a linear range of 10–50 mM with detection
limits of 38.8 nM (1) and 15.9 nM (3). Furthermore, the electrochemical reduction of hydrogen peroxide
rsc.li/njc in the same linear range as above showed limits of detection (3s) of 14.4 mM (1) and 11.6 mM (3).

Introduction techniques are some of the simplest and effective ways.6 In the
electrochemical method, because of the electroactive nature of
In most of the chemical reactions, hydrogen peroxide (H2O2) is H2O2, the electrons generated during the catalytic reaction are
formed as the intermediate or final product,1 and it is con- measured;7 in the optical method, photons emitted are taken into
sidered to be one of the most reactive oxygen species (ROS).2 account as these compounds show enhanced fluorescence property
As H2O2 is an unstable oxidant, it decomposes immediately in their aggregate state.6c
when in contact with edible items, causing serious health Many mediator-less electrochemical sensors that use enzymes
hazards3a such as cardiovascular diseases,3b neurodegenerative such as catalase and hemoglobin8 have shown high selectivity and
disorders,3c cancer,3d and diabetes.3e In certain cases, it can sensitivity towards H2O2 quantification. However, they possess
even damage proteins, DNA and RNA.4 The usage of such common drawbacks of being relatively expensive and unstable
potentially harmful chemical species as additives while processing (highly sensitive to thermal and chemical conditions during
food,5a beverages,5b milk,5c and soft drinks is quite common these electrode fabrication); as a result, even their storage and usage
days.5d Moreover, it is unfortunate that the detection of such low become difficult.9 Hence, to overcome such issues, looking for
concentrations of H2O2 is still a challenging task. Consequently, non-enzymatic H2O2 sensors would be a better option as these can
it is highly essential to develop a selective, sensitive, and reliable be used to detect H2O2 at a much lower potential, reducing
method to accurately quantify H2O2 present in various real the risk of other interfering electroactive species.10 Some of
samples. Numerous methods such as titrimetry,6a spectrometry,6b the mediator candidates such as inorganic nanomaterials,11
fluorescence,6c chemiluminescence,6d and the methods employing catalysts,12 metals, metal oxides,13 and carbon materials14 have
enzyme- and non-enzymatic electrodes6e can be used to determine been widely studied. In this series, a variety of metal-based
H2O2 levels; moreover, electrochemical and fluorescence sensing compounds such as hexacyanoferrates15 and ferrocene (Fc) and
its derivatives are also being explored as mediators.16 The
electrocatalytic oxidation response of an aromatic heterocyclic
Department of Chemistry, School of Advanced Sciences, Vellore Institute of
system that has been linked covalently to ferrocene moieties
Technology, Vellore 632 014, Tamil Nadu, India. E-mail: [email protected];
Tel: +91 9842639776
indicates that they are powerful mediators that can be used to
† Electronic supplementary information (ESI) available: Related spectra. See DOI: sense H2O2 via a reversible redox reaction (Fc/Fc+).17 Such
10.1039/c9nj01471c mediators are known to shorten the distance between the redox

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 8539--8550 | 8539
 View Article Online

Paper NJC

center of analytes and electrode surface, making the electron electron microscopy (HR-TEM) images were taken on FEI-Tecnai
transfer process much easier.18 Additionally, they also have G2 20 S-TWIN at an accelerating voltage of 200 kV. Before the
advantages such as good chemical stability and the lack of HR-TEM analysis, the sample was dropped on a Cu grid coated
dependence on pH and oxygen.19 These compounds are not with an ultrathin amorphous carbon film, and then dried under
just used as chemically modified working electrodes, but also ambient conditions. Infrared spectra were recorded on a PERKIN
as reference materials, which are known to show excellent SHIMADZU spectrometer spectrum One as KBr diluted discs.
chemical and electrochemical reversibility.20 UV-visible spectra were recorded using a JASCO UV-visible spectro-
Diverse luminescent materials that are AIE-active have been photometer using CH3CN as a solvent. Emission spectra were
specially designed and developed to work as sensors.21 Here, recorded using a Hitachi F-7000 FL Spectrophotometer. Electro-
the engineered AIE-active luminophores worked on the basic chemical measurements were performed on a CH-Instruments
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

principle of restricted intramolecular rotation (RIR).22 These Model CHI620E using an oxygen-free one-compartment cell with
are generally non-fluorescent in the solution state, but in the a platinum electrode as the working electrode, saturated Ag/AgCl as
aggregate or solid state, they become highly emissive.23 Based the reference electrode, and a platinum wire as the auxiliary
on this property, fluorescent sensors were developed in different electrode. CH3CN was used as the solvent and [N(C4H9-n)4]ClO4
fields to detect gases, pH, explosives and hazardous materials.24 was used as the supporting electrolyte. E1/2 values were calculated
For sensing H2O2, various fluorescent probes were explored, from (Epa + Epc)/2 (pa – anodic potential and pc – cathodic potential)
which showed stimuli-responsive aggregation and emission at a scan rate of 0.05 mV s1. Phosphate buffer solution (0.1 M)
behaviour.25 In the past, very few AIE fluorescent systems were made from K2HPO4 and KH2PO4 (in KCl) and adjusted to pH 7 was
developed for the detection of H2O2. Some fluoresceins include employed as the supporting electrolyte. Deionized water was used
pentafluorobenzenesulfonyl (PFBS),26 tetraphenylethylene (TPE)27 throughout the experiments.
and its derivatives (TPE-HPro)1 and L-lactate oxidase (TPE-HPro-
LOx)28 in aggregated/disaggregated states. Recently, it has been Preparation of the electrodes
reported that many fluorescent ferrocene-based probes as electron- To prepare the modified electrode, the ultrasonic technique
rich moieties work with the mechanism of photoinduced electron was used. One mg N-arylated bisferrocene pyrazole was dispersed
transfer (PET) to act as luminogens.29 Making use of this AIE in 1 mL of ethanol. From the prepared suspension, 4 mL was drop-
effect, so far, ferrocene-based molecules have been used as casted onto a bare screen-printed electrode and dried at room
chemical sensors.30 temperature. The electrochemical behavior of the sensor electrode
The current work focuses on developing novel ferrocene-based was studied using cyclic voltammetry at a potential window from
pyrazole derivatives for the efficient sensing of H2O2 through 1.0 to +1.0 at various scan rates in a phosphate buffer solution
electrochemical and optical methods, thus making use of their (PBS) with and without H2O2. The electrochemical oxidation of
dual properties of acting as outstanding redox mediators and redox peaks showed an increase in the concentration of H2O2
effective AIE luminogens. from 10 to 50 mM. Thus, the optimum potentials were selected as
0.25 V to 0.0 V (1) and 0.4 V to 0.5 V (3) for the electrochemical
sensing studies.
Experimental
Turn-off fluorescence detection of H2O2
Materials and procedures
The stock solution (100 mM) was made freshly after dissolving
The ferrocenyl pyrazole and C–N cross-coupling derivatives
11 mM of 30% H2O2 in 989 mM of deionized water. The growth
(1–4) were synthesized following previously published proce-
solution consisted of 1.0  104 M in 0.1 M phosphate buffer
dures.31,32 All reactions were carried out using an anhydrous
solution (PBS, pH 7) and different concentrations of H2O2
solvent unless otherwise noted. DCM was dried over calcium
(10–50 mM). The fluorescence intensities were recorded with
hydride. All results were observed by thin layer chromatography
excitation at 237 nm for 1 and 242 nm for 2.
(TLC plates). Products were isolated by column chromatography
(Avara silica gel 60–120 mm). Commercially available chemicals
Determination of the quantum yield
were purchased from TCI and Sigma-Aldrich Chemicals.
The fluorescence quantum yields (F) were determined by
Measurements eqn (1) relative to tryptophan (Fst = 0.14 in H2O).3
     2
The 1H, 13C and 19F NMR spectra were recorded in CDCl3 Ast Ix Z
solutions at 298 K using a BRUKER (400 MHz) spectrometer. Fx ¼ Fst    x2 (1)
Ax Ist Zst
All NMR spectra were reported in parts per million (ppm, d)
relative to tetramethylsilane ((CH3)4Si), with the residual solvent here, ‘‘x’’ and ‘‘st’’ stand for unknown and standard (tryptophan)
proton resonance and carbon resonances used as internal stan- samples, respectively; F is the quantum yield, A is the absorbance,
dards and integrations are reported as the number of protons. F is the total area of the fluorescence spectra, Z is the refractive
EI-Mass spectra were recorded by the electron ionization (EI) index of the solvents, and I is the area under the fluorescence
method on JEOL GCMATE II GC-MS. PerkinElmer CHN-2400 was spectra on an energy scale. The fluorescence lifetime measure-
used for micro elemental analyses. High-resolution transmission ment was carried out using a single photon counting method.

8540 | New J. Chem., 2019, 43, 8539--8550 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
 View Article Online

NJC Paper

The fluorescence decay curve was measured by exciting the (400 MHz, CDCl3): d = 2.664 (s, 6H, 2CH3), 4.034 (s, 10H,
molecule to 290 nm using o200 ps light of a nanoLED. 2C5H5), 4.253 (s, 4H, (H3, H4) of two C5 H4 rings), 4.619
(s, 4H, (H2, H5) of two C5H4 rings), 6.261 (s, 2H, 2CH), 8.081
General procedure for Chan–Lam coupling (s, 4H, C6H4) ppm. 13C NMR (100 MHz, CDCl3): d = 167.63,
To a stirred solution of ferrocenyl pyrazole (2 mmol) in dichloro- 154.41, 145.09, 136.61, 130.76, 109.10, 69.57, 69.38, 67.34,
methane (2 mL), 1,4-phenylenediboronic acid (3 mmol) was 14.63 ppm. MS (EI): m/z (M+) = 662.11.
added, followed by the desired amount of copper catalyst (1,4-Phenylene)bis((5-ferrocenyl-3-(trifluoromethyl)-1H-pyrazol-
(0.05 mmol). The reaction mixture was stirred at room tempera- 1-yl)methanone) (4). According to the general procedure, yield
ture in a vessel open to air. After 16 h, the reaction was quenched 63.0%. M.p. = 246.0–247.3 1C. Anal. calcd for C36H24F6Fe2N4O2:
by the addition of a saturated aqueous solution of ammonium C, 56.13; H, 3.14; N, 7.27. Found: C, 55.12; H, 3.36; N, 7.43%.
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

chloride. UV-Vis (nm, in CH3CN): lmax 238, 274, 451. Fluorescence: (lex =
1,4-Bis(3-ferrocenyl-5-methyl-1H-pyrazol-1-yl)benzene (1). 242 nm, lem = 306 nm, CH3CN). FT-IR (KBr disk): n(CH) 3226 (br,
According to the general procedure, yield 68.0%. M.p. = 156.0– m), n(CQO) 1724, n(CQN) 1612(vs), n(CQC) and n(C–N) 1500 (m),
157.5 1C. Anal. calcd for C34H30Fe2N4: C, 67.35; H, 4.99; N, 9.24. 1409 (vs) and 1276 (s) cm1. 1H NMR (400 MHz, CDCl3): d = 4.132
Found: C, 66.82; H, 5.22; N, 8.96%. UV-Vis (nm, in CH3CN): lmax (s, 10H, 2C5H5), 4.321 (s, 4H, (H3, H4) of two C5 H4 rings), 4.766
237, 297, 451. Fluorescence: (lex = 237 nm, lem = 352 nm, (s, 4H, (H2, H5) of two C5H4 rings), 6.312 (s, 2H, 2CH), 8.122
CH3CN). FT-IR (KBr disk): n(CH) 3084 (br, m), n(CQN) 1556 (s, 4H, C6H4) ppm. 13C NMR (100 MHz, CDCl3): d = 170.63, 158.63,
(vs), n(CQC) and n(C–N) 1516 (m), 1367 (vs) and 1192 (s) cm1. 146.16, 136.61, 130.77, 116.36, 108.12, 69.87, 69.54, 69.35,
1
H NMR (400 MHz, CDCl3): d = 2.314 (s, 6H, 2CH3), 4.066 (s, 10H, 67.3 ppm. 19F NMR (376 MHz, CDCl3): 62.18 ppm. MS (EI):
2C5H5), 4.252 (s, 4H, (H3, H4) of two C5 H4 rings), 4.601 (s, 4H, m/z (M+) = 770.05.
(H2, H5) of two C5H4 rings), 6.087 (s, 2H, 2CH), 7.402 (s, 4H,
C6H4) ppm. 13C NMR (100 MHz, CDCl3): d = 147.39, 139.35,
102.20, 93.38, 69.92, 69.54, 68.57, 66.49, 12.26 ppm. MS (EI): m/z
Results and discussion
(M+) = 606.12. Synthesis and spectral properties
1,4-Bis(5-ferrocenyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzene A straightforward route can be the direct C–N cross-coupling of
(2). According to the general procedure, yield 59.0%. M.p. = 146.0– new N-arylated bisferrocene pyrazole synthesized according to
147.2 1C. Anal. calcd for C34H24F3Fe2N4: C, 57.17; H, 3.39; N, 7.84. Schemes 1 and 2. The Chan–Lam and Buchwald–Hartwig
Found: C, 57.51; H, 3.74; N, 7.23%. UV-Vis (nm, in CH3CN): lmax reactions are two related methods that are widely practiced
237, 274, 445. Fluorescence: (lex = 237 nm, lem = 312 nm, CH3CN). for this purpose. The synthesis approach to N-arylated bisfer-
FT-IR (KBr disk): n(CH) 3145 (br, m), n(CQN) 1606 (vs), n(CQC) rocene pyrazoles 1–4 with donor–acceptor–donor structures,
and n(C–N) 1506 (m), 1369 (vs) and 1255 (s) cm1. 1H NMR including all derivatives of compound 3, has been reported
(400 MHz, CDCl3): d = 4.144 (s, 10H, 2C5H5), 4.195 (s, 4H, (H3, earlier.33 All these compounds were characterized by obtaining
H4) of two C5 H4 rings), 4.275 (s, 4H, (H2, H5) of two C5H4 rings), their melting points as well as by conducting CHNS, EI-Mass,
6.797 (s, 2H, 2CH), 7.420 (s, 4H, C6H4) ppm. 13C NMR (100 MHz, FT-IR, 1H, 13C and 19F NMR spectral studies. The elemental
CDCl3): d = 151.23, 148.76, 143.09, 138.20, 127.97, 125.31, 104.15, analyses (CHNS) of all the compounds showed that the calcu-
72.17, 68.99, 65.99 ppm. 19F NMR (376 MHz, CDCl3): 62.16 ppm. lated and found values for carbon, hydrogen and nitrogen
MS (EI): m/z (M+) = 714.06. confirmed the purity of these compounds.
The 1H, 13C and 19F NMR results of the synthesized com-
General procedure for Buchwald–Hartwig cross-coupling
pounds 1–4 were recorded in CDCl3 at room temperature using
A pyrex screw tube was capped with a Teflon septum and a stir TMS as the internal standard; the spectra are displayed in
bar was charged with Pd(dba)2 (0.0125 mmol), bis(diphenyl- Fig. S1–S10 (ESI†), and the results of the compounds are
phosphino)methane (DPPM) ligand (0.0250 mmol), terephthaloyl consistent with literature results.33,34 The 1H NMR spectra of
chloride (1.25 mmol), ferrocenyl pyrazole (1.50 mmol), and tBuONa the compounds show several sets of signals. The ferrocene
(1.75 mmol). The tube was displaced and flushed with nitrogen protons appear at similar positions (d = 4.19 ppm for the
and then placed in a preheated oil bath (110 1C) for 24 h. After unsubstituted rings and d = 4.25–4.65 ppm for the substituted
completion of the reaction, the tube was allowed to cool room rings). The singlet peaks at d = 2.31–2.66 ppm are associated
temperature. The reaction mixture was purified by silica gel with the N-bound methyl (–CH3) protons. The pyrazole ring
column chromatography to provide the desired compound. proton signals appear at d = 6.08–7.79 ppm. For compounds
(1,4-Phenylene)bis(1-(5-methyl-3-ferrocenyl-1H-pyrazol-1-yl)- 1–4, the appearance of a singlet at about d = 7.40–8.12 ppm is
methanone) (3). According to the general procedure, yield
72.0%. M.p. = 268.0–269.4 1C. Anal. calcd for C36H30Fe2N4O2:
C, 65.28; H, 4.57; N, 8.46. Found: C, 64.30; H, 4.63; N, 8.24%.
UV-Vis (nm, in CH3CN): lmax 234, 288, 454. Fluorescence:
(lex = 242 nm, lem = 321 nm, CH3CN). FT-IR (KBr disk):
n(CH) 3080 (br, m), n(CQO) 1683, n(CQN) 1589 (vs), n(CQC)
and n(C–N) 1537 (m),1344 (vs) and 1271 (s) cm1. 1H NMR Scheme 1 C–N cross coupling Chan–Lam.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 8539--8550 | 8541
 View Article Online

Paper NJC

Scheme 2 C–N cross coupling Buchwald–Hartwig amination.

due to the aromatic protons, which provides evidence for the

successful C–N cross-coupling. Furthermore, the 13C NMR data
for compounds 1–4 revealed an intense singlet at d = 66–68 ppm
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

for the unsubstituted cyclopentadienyl ring Z5-C5H5 carbons of

ferrocene as well as two signals at d = 69–72 ppm due to the
substituted cyclopentadienyl ring Z5-C5H5. The carbonyl signals of
3 and 4 due to the ferrocenyl pyrazole-bound CQO moiety are seen
at d = 169–170 ppm. Moreover, all the distinctive resonances of the
aromatic carbon atoms showed up as two sets of closely spaced
singlets at d = 127.97, 129.3 ppm and d = 136.0–139.35 ppm for Fig. 1 UV-vis absorption spectra of N-arylated bisferrocene pyrazole
the ortho, meta, para and quaternary carbons, respectively. The 1–4.
values of 19F chemical shifts for –CF3 may be used to identify the
environment around the fluorine atoms. For compounds 2 and 4,
in the wavelength range of 200–1500 nm. It is beneficial to
resonances are observed at 62.16 and 62.18 ppm, respectively.
understand the electronic state, optical absorption or trans-
EI-Mass spectra studies showed a peak with the expected isotopic
mittance window and cut-off wavelength of the compounds.
patterns at m/z = 606.1204 (for 1), 714.0612 (for 2), 662.1101 (for 3)
The transfer of charge involving the compound was from 300 to
and 770.0510 (for 4), and the obtained data coincided with the
900 nm, which proved that there is absorption in most of the
calculated data, as shown in Fig. S11–S14 (ESI†).
visible region, as shown in Fig. 1.
The FT-IR spectra of compounds were recorded in the region
The relation between the absorption coefficient (a) was calcu-
of 4000–400 cm1 to provide information for the vibrational
lated using the Kubelka–Munk equation39 and the incident
modes (Fig. S15, ESI†). One of the weak C–H stretching absorp-
photon energy (hn) was determined using Tauc’s relationship in
tion bands of the aromatic phenyl ring in the 3100–3090 cm1
the high absorption region of semiconductors as follows:
range can be observed in all the compounds. The intense
absorption bands of 3 and 4 in the 1725–1650 cm1 range are ahn = a0(hn  Eg)m (2)
due to the n(CQO) stretching mode of the carbonyl groups.35 Apart
from these, the strong characteristic bands at 1600–1580 cm1 and (ahn)2 = A(hn  Eg) (3)
1550–1500 cm1 for the compounds 1–4 confirm the presence of
n(CQC) and n(CQN), respectively, for the pyrazole moiety. All the Here, a0 is an energy-independent constant (sometimes
other additional bands observed in the IR spectra belong to called the band tailing parameter) and Eg is the optical energy
the aromatic substituents and the characteristic peak for Fe–C gap, which is situated between the localized states near the
associated with the ferrocene group can be found in the range of mobility edges according to the Mott and Davis model of the
485–470 cm1.36 density of states.40 In eqn (2), there is another constant (m),
which is called the power factor of the transition mode. It is
Optical properties dependent on the crystalline or amorphous nature. To deter-
The UV-vis absorption spectra of N-arylated bisferrocene pyrazole mine the optical energy gap, Eg, of the investigated N-arylated
were examined in CH3CN solutions (104 M) in the wavelength bisferrocene pyrazole, one can plot (ahn)2 versus the photon
range of 200–800 nm; the absorptions were observed at 237– energy (hn) using the optical absorption data, as shown in
280 nm, 360–375 nm and 440–455 nm and are shown in Fig. 2. The energy gaps for the title compounds were found to
Fig. S16 (ESI†). The highest energy absorption band in the be 3.1 eV (1), 2.1 eV (2), 2.5 eV (3) and 2.1 eV (4), which
region of 240–320 nm can be ascribed to a high energy ligand- suggested that they may be used in visible-light response
center p–p* electronic transition.33,37 The lowest absorption devices and photovoltaic devices.41 It was observed that optical
bands at 320–365 nm correspond to the n–p* transition in 3 bandgap values agreed with the electrochemical measurement
and 4 from carbonyl group intramolecular charge transfer (ICT) results in Table 3.
excitations. The lower energy (LE) bands at 440–455 nm are The synthesised N-arylated bisferrocene pyrazole 1–4 were
from the localized excitation either by a Fe(II) d–d transition or characterized by fluorescence spectroscopy in a CH3CN solvent
by a metal–ligand charge transfer (MLCT) band (dp–p*);38 hence, (104 M). The fluorescence was readily observed (Fig. S17, ESI†)
the band at 440–455 nm may possess some ferrocene-like character. with an emission maximum at 350 nm. The C–N cross-coupling
In order to calculate the optical band gap of N-arylated bisferrocene of 1 and 3 induced significant red-shift of the emission maxima
pyrazole 1–4, diffuse reflectance spectroscopic methods were used compared with those of 2 and 4 because the C–F bond in the

8542 | New J. Chem., 2019, 43, 8539--8550 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
 View Article Online

NJC Paper
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

Fig. 3 Cyclic voltammograms obtained for ferrocene and N-arylated

2 1 2
Fig. 2 Plots of (ahn) (eV m ) versus photon energy hn for N-arylated bisferrocene pyrazole 1–4 in the presence of 0.1 M TBAP in solution
bisferrocene pyrazole 1–4. (0.1 V s1) in 105 M CH3CN solutions.

trifluoromethyl moiety could suppress the non-radiative process was observed implied a simultaneous two-electron transfer at the
and cause a blue shift.42 The emission peaks were observed at same potential of the ferrocenyl subunits and indicated that the
352 (1), 312 (2), 321 (3) and 306 (4) nm and excitation peaks were two ferrocenes in 1–4 behave independently.34,45b This is attri-
observed at 237 and 242 nm. A very weak fluorescence spectrum buted to the fact that the strong electron-withdrawing effect of the
was obtained due to the presence of ferrocene.43 The incomplete trifluoromethyl substituent in the compounds 2 and 4 enables
recovery of fluorescence in compounds 1–4 was because of the fast electron transfer from ferrocene to the pyrazole ring.46a
energy transfer quenching by the ferrocenium ion on the mole- A more anodic shift was observed from the oxidation of com-
cules. However, the oxidation of the side group (ferrocene - pounds 1–4 in the range of 654–730 mV, when compared with
ferrocenium) indicated that the possible electronic interaction ferrocene (532 mV) at identical conditions, indicating one-
occurred intramolecularly in the system, as has been reported electron transfer (DEP = 63–79 mV) from the ferrocene/ferroce-
previously.44 The Stokes shifts of 1 (40 nm) became greater nium (FeII - FeIII) couple in the compounds 1–4.44a The shift in
compared to those of 2–4. The fluorescence quantum yields (FF) the positive oxidation potentials in compound 4 was due to the
of 1–4 in acetonitrile were low (1 and 3 = 0.02, 2 and 4 = 0.01), electron-withdrawing effect which makes more anodic Eox and
which indicated the ability to act as a donor and acceptor. cathodic Ered values compared to 1.44b The overall anodic shift in
the oxidation potential of ferrocene was due to the substituent
Cyclic voltammetry effect of the pyrazole subunits. Furthermore, from the oxidation (Eox)
and reduction (Ered) potentials, the HOMO and the LUMO energy
The electrochemical features of compounds 1–4 were investigated
levels were calculated using the relationships EHOMO = (Eox + 4.4)
by cyclic voltammetry in an acetonitrile solution containing
and ELUMO = (Ered + 4.4), respectively.46b
[N(C4H9-n)4]ClO4 as the supporting electrolyte. All measure-
ments were carried out in 105 M solutions at room tempera-
ture in the potential range from 0 to 1.0 V at a scan rate of Solvatochromism
0.05 mV s1. The electrochemical data for these compounds are The photophysical properties of N-arylated bisferrocene pyrazole
summarized in Table 2; it can be seen that N-arylated bisferro- derivatives were studied in various solvents and are presented
cene pyrazole exhibits one-electron redox couple and the redox in Fig. S18–S21 (ESI†); all the data are listed in Table S1 (ESI†).
potentials shift to a positive potential in comparison with the We observed that the polarity of solvents strongly influenced
observation for unsubstituted ferrocene. Cyclic voltammograms the photophysical properties of N-arylated bisferrocene pyrazole
(CV) of solutions containing 1–4 show a chemically reversible derivatives. As the solvent polarity increased from nonpolar to
oxidation process with current ratio ipa/ipc equal to unity; more- polar solvents, the absorption bands of N-arylated bisferrocene
over, the half-wave potential values [E1/2 = (Epa + Epc)/2] of all pyrazole derivatives were almost identical because the ground-
compounds were more positive, as shown in Fig. 3. The E1/2 values state electronic structure and small dipole moments associated
were identical within the experimental errors to that of the Fc/Fc+ with the ICT transitions are independent of solvent polarity.47 The
couple (E1/2 = 492 mV) taken as the internal reference. The anodic solvatochromism behaviour of compounds are a good correlation
to cathodic peak-to-peak separations were similar to that observed with p* values by Kamlet and Taft parameters with increase the
for ferrocene under identical conditions, indicating that it is likely solvent polarity.48 Compounds 1 and 2 in the CHCl3 solvent show
that one-electron delocalization increases and the potential absorbance bands at 291 nm (1) and 289 nm (2); moreover, with
changes positively.45a The fact that only a single oxidation wave the increase in solvent polarity, red shifts are observed in the

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 8539--8550 | 8543
 View Article Online

Paper NJC

Table 1 UV-visible absorption, fluorescence, quantum yield and lifetime data for 1–4

Entry lmax,absa (nm), e (105 M1 cm1) lmax,flb (nm) Stokes shiftc (nm) Quantum yield (Ffl)d AIE quantum yield (H2O/CH3CN) (Ffl)d tfc (ns)
Compound 1 237 (5.0), 293 (4.2), 451 (0.2) 314, 352 9675, 6237 0.02 0.03 (60%) 3.25
Compound 2 237 (5.0), 274 (4.4), 445 (0.2) 312, 335 9579, 5938 0.01 0.03 (60%) 3.62
Compound 3 234 (4.8), 288 (3.7), 454 (0.2) 322, 389 9029, 3680 0.02 0.04 (60%) 4.53
Compound 4 238 (4.9), 274 (2.8), 450 (0.1) 306, 335 10 506, 12 813 0.01 0.04 (60%) 3.92
a
The UV-visible and FL experiments were performed in CH3CN solvents. b Excitation at either 235 or 240 nm. c Dss = UV-visible and FL quantum
yields were reported relative to tryptophan (Ffl = 0.14 in water). d Fluorescence lifetime was measured by exciting the samples at 290 nm using the
time-correlated single-photon-counting technique using 150 ns nanoLEDs.
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

Table 2 Cyclic voltammetry data (potentials vs. Fc/Fc+), scan rate These compounds could be aggregated in an aqueous mixture;
0.05 mV s1 at the platinum electrode of 0.5 mmol L1 solution of thus, the emission spectra of the compounds were recorded
ferrocene and N-arylated bisferrocene pyrazole in dry acetonitrile with
in the presence of different water fractions ( fw = 0–90%),
0.1 mol L1 of nBu4NClO4 as the supporting electrolyte at 25 1C
maintaining the overall concentration of the solution at 104 M.
Entry Epa (mV) Epc (mV) ipc/ipa (mV) E1/2 (mV) DE (mV) In this regard, the intramolecular torsion is relatively free, which
Ferrocene 532 453 0.91 492 79 accelerates the non-radiative pathway25 and affords weak fluores-
Compound 1 654 588 0.92 621 66 cence. In the aggregated state, the emission behaviour is
Compound 2 730 652 0.89 691 78
enhanced due to the restriction of intramolecular rotation.30
Compound 3 708 639 0.86 673 69
Compound 4 689 626 0.92 659 63 Based on this concept, we studied the emission behaviours of
all synthesized compounds and observed the aggregation process
by increasing the percentage of water (Fig. 4–7). However, up to
Table 3 Comparison of experimental (CV/UV-Vis) HOMO–LUMO energy 40%, 1–4 nearly showed weak emissions at 359 (1), 315 (2),
296 (3), and 343 (4) nm in CH3CN, respectively. The maximum
Experimental data
fluorescence was obtained at water fractions of 40–60%. The
Entry la (nm) EHOMOb (eV) ELUMOc (eV) Eoptica1
g
d
(eV)
fluorescence intensity increased significantly, and all compounds
Compound 1 491 5.054 2.529 2.525 1–4 showed enhancement up to a water fraction of fw o 60%.
Compound 2 479 5.130 2.542 2.588 This aggregation was followed by decrease on increasing the
Compound 3 483 5.108 2.541 2.567
Compound 4 475 5.089 2.479 2.610 water fraction up to fw o 90% with the appearance CH3CN
a
solution in the form of a new peak at fw = 60% lmax = 351 (1),
Calculated as lonset values from absorption graphs in CH3CN. b Calcu-
lated as HOMO and LUMO levels obtained from CV using EHOMO = 306 (2), 303 (3) and 347 (4) nm. When the water fraction was at
e[Eonset
ox + 4.4]. c Eoptical onset values obtained from oxidation peak in 60%, the fluorescence intensity of the mixture reached maximum
cyclic voltammogram. ELUMO = Eoptical g + EHOMO. d Calculated as optical with 8-fold (1), 7-fold (2), 8-fold (3) and 4-fold (4) enhancements,
band gap calculated from absorption onset/edge using the equation
e[Eoptical ] = 1240/lonset. which were higher than that in CH3CN ( fw = 0%). Furthermore,
g
for compounds 1 and 2, when the water fraction ( fw) was
increased from 0% to 90%, a blue shift with the enhanced
absorbance bands to 295 nm (1) and 293 nm (2) for DMF and ACN,
respectively. In this case, positive solvatochromism is observed
and a maximum peak is seen in polar solvents compared to the
observation for nonpolar solvents, which suggests that the HOMO–
LUMO gap becomes narrow for polar solvents. These results
indicate that compounds 1 and 2 are more solvated in the excited
state than in the ground state. The absorption spectra of com-
pounds 3 and 4 exhibit a moderate hypsochromic (blue) shift as
the solvent polarity increases (labs,max = 291 nm in CHCl3, labs,max =
295 nm in DMSO). The extent of this effect is not the same in case
of compounds 3 and 4 belonging to this group containing electron-
withdrawing groups such as –CF3 moieties, which have a low-lying
n–p* excited state.49 The increase in the polarity of the medium
caused a hypsochromic shift in the absorption bands of 3 and 4
recorded in all studied solvents. It was coupled with the negative
solvatochromism of the probes that resulted from the decrease in
dipole moment.

Aggregation-induced emission
Fig. 4 The PL spectra of N-arylated bisferrocene pyrazole (1) in different
The AIE properties of compounds 1–4 were investigated water fractions (fw) at a concentration of 1  104 M (excitation wave-
using different water fractions ( fw) in CH3CN/water mixtures. length: 237 m).

8544 | New J. Chem., 2019, 43, 8539--8550 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
 View Article Online

NJC Paper
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

Fig. 5 The PL spectra of N-arylated bisferrocene pyrazole (2) in different Fig. 7 The PL spectra of N-arylated bisferrocene pyrazole (4) in different
water fractions (fw) at a concentration of 1  104 M (excitation wave- water fractions (fw) at a concentration of 1  104 M (excitation wave-
length: 237 nm). length: 242 nm).

1–4 were FF = 0.01 (2, 4) and 0.02 (1, 3). The restriction of
intramolecular rotations (RIR) in compounds 1–4 shows
increased the PL intensity due to the AIE effect, which resulted
in an increase in the quantum yield.52 When the water content
of the acetonitrile–water system was 60%, the quantum yields
increased to FF = 0.03 (1–2) and FF = 0.04 (3, 4), which were
four times higher than those in the acetonitrile solution for
compounds 3 and 4.

Time-resolved fluorescence
The AIE behaviours of N-arylated bisferrocene pyrazole deriva-
tives 1–4 were investigated to study the excited state dynamics.
Fluorescence lifetime (t) was investigated by the time-correlated
single photon counting method by exciting the sample with
280 nm, 150 ps pulse using nanoLEDs. By using this technique,
one can deduce the excitation lifetime of the molecule, i.e., how

Fig. 6 The PL spectra of N-arylated bisferrocene pyrazole (3) in different

water fractions (fw) at a concentration of 1  104 M (excitation wave-
length: 234 nm).

intensity of emission was observed. For the compounds 3

and 4, with an increase in fw from 0% to 90%, the discharge
red-shifted because of the enhanced electron-releasing effect of
the ferrocenyl substituent, which is directly attached to the
carbonyl group. The excited intramolecular motions in 1–4 may
be considered as one of the possible reasons for AIE. Apparent
intramolecular charge transfer (ICT) characteristics were
verified in these compounds.50 The increase in the PL inten-
sity of compounds 1–4 resulted in increased emission as well
as an increase in the quantum yield; moreover, the quantum
yields were calculated in acetonitrile and acetonitrile–water
systems using tryptophan as a standard.51 The observed Fig. 8 Time-resolved luminescence spectra of N-arylated bisferrocene
quantum yields in 0% acetonitrile solution for compounds pyrazole 1–4 in the CH3CN/water mixture (40 : 60) excited at 290 nm.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 8539--8550 | 8545
 View Article Online

Paper NJC
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

Fig. 9 Fluorescence emission spectra of N-arylated bisferrocene pyra- Fig. 10 Stern–Volmer plots of N-arylated bisferrocene pyrazole 1.
zole 1 AIE-luminogens in CH3CN/water mixture (40 : 60) excited at 237 nm
with different concentrations of H2O2 (0–50 mL).
materials were capable of detecting H2O2 by an aggregation-
induced emission method. The origin of fluorescence quench-
long the molecule stays excited. Moreover, the measurement of ing in H2O2 was ascribed to a photoinduced electron transfer
fluorescence lifetime is more robust than the extent of fluores- between ferrocene and ferrocenium ions.29 In order to detect
cence intensity because it depends neither on the strength of the H2O2, we have examined the probes of N-arylated bisferro-
excitation nor on the concentration of the fluorophore.53 The cene pyrazoles 1–4 (containing 50% CH3CN/H2O in a ratio of
decay profiles of N-arylated bisferrocene pyrazole derivatives 1–4 40 : 60 v/v) showing a consistent emission peak in acetonitrile/
in a CH3CN/water mixture (40 : 60) are shown in Fig. 8. The decay water mixtures. To detect H2O2, the compounds were treated
profiles can be fitted with a single exponential function. The with H2O2 in a PBS buffer solution (containing 50% CH3CN/
lifetime data are summarized in Table 1. The fluorescence life- H2O in the ratio of 40 : 60 v/v), and further shifted emission
times of 1–4 were measured to be 3.25, 3.62, 4.53 and 3.92 ns, bands were observed. The quenching spectra of compounds 2
respectively. The observed longer fluorescence lifetime indicated and 4 showed less detection of H2O2 (Fig. S22 and S23, ESI†).
aggregation of the N-arylated bisferrocene pyrazole molecules. It This can be explained by the fact that the electron-deficient
should be noted here that 1–4 in the mixture (CH3CN/water) –CF3 moiety on the pyrazole ring has much stronger electron-
furnish identical fluorescence lifetimes, indicating that the withdrawing ability, leading to the decrease in the energy
formed aggregates are not affected by the surrounding solvent barrier of the intramolecular charge transfer (ICT). AIE-active
molecules. luminogens can be quenched with the addition of H2O2,
i.e., the emission intensities of all compounds decrease. The
AIE-active fluorescence responses to H2O2 emission intensity of N-arylated bisferrocene pyrazole is
expected to follow the quenching effect; this can be described
The fluorescence spectra of compounds 1–4 were recorded and
by the Stern–Volmer equation,54 in which I0 and I represent the
it was interesting to find that the AIE luminogens as turn-on

Table 4 Comparison of the analytical characteristics of some proposed methods for the electrochemical and fluorescence determination of H2O2 using
different modified electrodes

Materials Potential Linear range Detection techniques Detection limit

Fc@PANI 0.56 4–64mM Cyclic voltammetry 4 mM [ref. 20]
Fc@CNT 0.50 5–500 mM Cyclic voltammetry 5 mM [ref. 16]
Fc@graphene 0.50 5–4.75 mM Cyclic voltammetry 4.15 mM [ref. 18]
poly(DA-Fc) 0.55 10–20 mM Cyclic voltammetry 5 mM [ref. 57b]
Fc-TH 0.3 0.569–785 mM Cyclic voltammetry 0.190 mM [ref. 36]
FcAPS/GCE 0.60 10–10 mM Cyclic voltammetry 2.07 mM [ref. 19]
Fc@RTIL 0.90 — Cyclic voltammetry 50 mM [ref. 17]
MDMO–PPV — 1.5  107–2.2  105 M Fluorescence 8.5  108 M [ref. 57]
TPE — 10–110 mM Fluorescence 180 nM [ref. 27]
TPE-HPro — 0–100 mM Fluorescence 100 nM [ref. 1]
TPE-HPro-LOx — 0–200 mM Fluorescence 5.5 mM [ref. 28]
Bis-Fc-Pz/SPE 0.41 10–50 mM Cyclic voltammetry 14 mM (1) and 11 mM (3) (this work)
Bis-Fc-Pz — 10–50 mM Fluorescence 38.8 nM (1) and 15.9 nM (3) (this work)

8546 | New J. Chem., 2019, 43, 8539--8550 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
 View Article Online

NJC Paper

steady-state fluorescence intensities in the absence and pyrazole obtained from the slope of the Stern–Volmer plots are
presence of H2O2, respectively. 2.57  108 for compound 1 and 2.04  107 for compound 3.
The linear and non-linear Stern–Volmer equation proves The excellent quenching efficiency of N-arylated bisferrocene
that the entire replacement of AIE-active luminogens is bound pyrazole is supported by an extremely low limit of detection for
to increase the concentration from 10 to 50 mM, which is better H2O2 (as shown in the inset of Fig. 9 and 11). The detection limit
than that reported for ferrocene-based probes. (LOD) is defined by the equation 3s/s with a signal-to-noise ratio
I0 of 3, where s is the standard deviation of the blank signals (n = 3)
¼ 1 þ KSV ½Q (4) and s is the slope of the calibration curve.1,55 Based on this
I
equation, the detection limits (LODs) of H2O2 were estimated to
The Stern–Volmer KSV is the Stern–Volmer quenching con- be 38.8 (1) and 15.9 (3) nM. A comparative study was also carried
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

stant and [Q] represents the concentration of the quencher out to show the advantages and better LODs of our detection
H2O2. The Stern–Volmer plot illustrates that the quenching of system over those of previously reported H2O2 sensors (Table 4).
H2O2 bound by AIE-active compounds 1 and 3 is in good
agreement (R = 0.996 and 0.942). The binding constants,
as shown in Fig. 10 and 12 (Ksv), of N-arylated bisferrocene

Fig. 11 Fluorescence emission spectra of N-arylated bisferrocene

pyrazole 3 AIE-luminogens in CH3CN/water mixture (40 : 60) excited at Fig. 13 The HR-TEM images of compounds 1 and 3 indicate the size of
237 nm with different concentrations of H2O2 (0–50 mL). the quantum dots to be around 3–5 nm.

Fig. 14 Cyclic voltammetry of N-arylated bisferrocene pyrazole 1-

modified SPE electrode in 0.1 M PBS (pH 7.0) containing 10 mM H2O2 at
different scan rates. Inset is the calibration curve of the error bars, which
Fig. 12 Stern–Volmer plots of N-arylated bisferrocene pyrazole 3. represent the standard deviation for three independent measurements.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 8539--8550 | 8547
 View Article Online

Paper NJC

which could result in the aggregated state. Unsurprisingly, the

PL intensities increased with the addition of water. With this
AIE phenomenon, considering that the interactions between
water and solvent molecules dictate the non-radiative decay, we
assumed that aggregation must deactivate non-radiative emission.25
For the non-aggregated quantum dots uniformly dispersed in the
solution, a significant amount of excitation was non-radiatively
dissipated in the surrounding solvent. When aggregated, the
interactions between the AIE dots at the center of the aggregates
and solvent molecules were reduced. The water molecules were
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

surrounded by CH3CN, leading to the aggregation of quantum dots;

thus, the PL intensity enhanced significantly.

Electrochemical detection of H2O2

The electrocatalytic activity of N-arylated bisferrocene pyrazole
Fig. 15 Cyclic voltammetry of N-arylated bisferrocene pyrazole 3- towards H2O2 reduction was evaluated by the cyclic voltammetry
modified SPE electrode in 0.1 M PBS (pH 7.0) containing 10 mM H2O2 at
technique. Herein, the screen-printed electrode was modified with
different scan rates. Inset is the calibration curve of the error bars, which
represent the standard deviation for three independent measurements.
N-arylated bisferrocene pyrazole using the drop-coating method
and the peak potential was varied from 1 V to 1.0 V vs. Ag/AgCl.
The current response was obtained at a scan rate of 50 mV s1.
The peaks at 0.25 to 0.0 V (1) and 0.4–0.5 V (3) appeared to
Aggregation of quantum dots
forward and the detection of hydrogen peroxide concentration of
The quantum dots of compounds 1 and 3 were studied by 1.0  104 at scan rate 50 mV s1 vs. Ag/AgCl. The possible
HR-TEM and showed better sensing of H2O2 than those of 2 mechanism is that both compounds lead to the reduction of H2O2
and 4. HR-TEM helped confirm the size and morphology of to OH using the redox couple of Fc/Fc+,17 as shown in Fig. 16.
the quantum dots. The aggregation enhanced PL emission This mechanism was likely a function of the amount of time each
response between non-aggregate (0%) and aggregated (60%) (FeII - FeIII) ferrocenium ion persisted in the system, i.e., the
in water is confirmed by morphology changes in TEM images, magnitude of the difference in the rates of ferrocene redox
which show that there are no quantum dots at 0% water by ferrocenium through intramolecular electron transfer.56 The
(Fig. 13a and c) and addition of 60% water shows larger AIE N-arylated bisferrocene pyrazoles 1 and 3 (Fig. 14 and 15) showed
dots (Fig. 13b and d). From the HR-TEM images, the size of the good redox behaviours due to the presence of the 5-methyl-3-
AIE dots was confirmed to be 3–5 nm as well as the morphology, ferrocenyl-1H-pyrazole moiety, which helped donate electrons.

Fig. 16 (a) Electrode preparation and (b) schematic representation of the mechanism of H2O2 reduction.

8548 | New J. Chem., 2019, 43, 8539--8550 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
 View Article Online

NJC Paper

Compared with compounds 1 and 3, compounds 2 and 4 were not 2 K. Nitinaivinij, T. Parnklang, C. Thammacharoen, S. Ekgasit
very effective for the detection of H2O2 (Fig. S24 and S25 ESI†) and K. Wongravee, Anal. Methods, 2014, 6, 9816–9824.
because of a more steric and the most electronegative nature46b,57 3 (a) Y. Chen, W.-J. Zhu, X.-R. Wei, Y.-J. Xu, R. Sun and
due to the 3-ferrocenyl-5-(trifluoromethyl)-1H-pyrazole (–CF3) J.-F. Ge, Anal. Methods, 2018, 10, 3754–3758; (b) S. Phosri,
group. The hydrogen peroxide reduction potential is absent N. Jangpromma, R. Patramanon, B. Kongyingyoes,
in the case of bare electrodes, thereby proving that when P. Mahakunakorn and S. Klaynongsruang, Inflammation,
compounds 1 and 3 interacted with H2O2, they generated 2017, 40, 205–220; (c) M. T. Lin and M. F. Beal, Nature,
enhanced responses. Herein, sensing towards H2O2 of the 2006, 443, 787–795; (d) Z. Zhou, J. Song, L. Nie and X. Chen,
tried different addition and we found a dramatic increase in Chem. Soc. Rev., 2016, 45, 6597–6626; (e) N. Houstis,
the reduction peak potential upon the addition of H2O2 having E. D. Rosen and E. S. Lander, Nature, 2006, 440, 944–948.
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

concentrations from 10 to 50 mM. 4 E. Ma, P. Chen, H. M. Wilkins, T. Wang, R. H. Swerdlow and

The limit of detection (L.O.D) for the screen-printed modi- Q. Chen, Free Radical Biol. Med., 2017, 113, 36–47.
fied electrodes were found to be a Linear plot for concentration 5 (a) F. Mollarasouli, K. Asadpour-Zeynali, S. Campuzano,
vs. current gave R2 = 0.9999 and L.O.D. = 14.4 mM for (1); also, P. Yáñez-Sedeño and J. M. Pingarrón, Electrochim. Acta,
(3) showed R2 = 0.9999 and L.O.D. = 11.6 mM. These values 2017, 246, 303–314; (b) C.-L. Hsu, H.-D. Jang, M.-S. Su, K.-S.
exhibited a linear range with a reasonable detection limit when Chang and Y.-S. Huang, Eur. Food Res. Technol., 2008, 226,
we compared with previously reported values (Table 4). 809–815; (c) G. R. K. Reddy and P. S. Kumar, Mater. Sci. Eng., C,
2017, 75, 1480–1488; (d) D. Harms, J. Meyer, L. Westerheide,
B. Krebs and U. Karst, Anal. Chim. Acta, 1999, 401, 83–90.
Conclusion 6 (a) E. C. Hurdis and H. Romeyn, Anal. Chem., 1954, 26,
In the current work, a new class of N-arylated bisferrocene 320–325; (b) D. Wu, X. Deng, X. Huang, K. Wang and Q. Liu,
pyrazole derivatives (1–4) was successfully synthesized and J. Nanosci. Nanotechnol., 2013, 13, 6611–6616; (c) M. Abo,
characterized. Compounds 1 and 3 showed excellent dual Y. Urano, K. Hanaoka, T. Terai, T. Komatsu and T. Nagano,
properties of acting as AIE-luminogens and electrocatalytically J. Am. Chem. Soc., 2011, 133, 10629–10637; (d) S. Hanaoka,
active species; moreover, it is to be noted that compounds 1 J.-M. Lin and M. Yamada, Anal. Chim. Acta, 2001, 426, 57–64;
and 3 were AIE-active luminogens, showing strong intra- (e) M. Liu, R. Liu and W. Chen, Biosens. Bioelectron., 2013,
molecular charge transfer (ICT) between the pyrazole and 45, 206–212.
ferrocene moieties. The enhanced emission is the formation 7 B. Li, J.-B. Chen, Y. Xiong, X. Yang, C. Zhao and J. Sun, Sens.
of AIE-quantum dots in an aggregated state at 0% and 60% Actuators, B, 2018, 268, 475–484.
water. Compounds 1 and 3 were used to detect H2O2 with high 8 (a) M.-J. Song, S. W. Hwang and D. Whang, Talanta, 2010, 80,
sensitivity even at low concentrations (10–50 mM), while com- 1648–1652; (b) M. Shamsipur, M. Asgari, M. G. Maragheh and
pounds 2 and 4 showed no response because of the electro- A. A. Moosavi-Movahedi, Bioelectrochemistry, 2012, 83, 31–37.
negative fluorine atom and the bigger size of the CF3 moiety. 9 (a) Z. Bai, G. Li, J. Liang, J. Su, Y. Zhang, H. Chen, Y. Huang,
The results are comparable to those of the existing non- W. Sui and Y. Zhao, Biosens. Bioelectron., 2016, 82, 185–194;
enzymatic sensors, which are suitable for the fluorescence (b) Y. Shu, B. Li, J. Chen, Q. Xu, H. Pang and X. Hu, ACS
imaging of H2O2 in living cells. In this aspect, further studies Appl. Mater. Interfaces, 2018, 10, 2360–2367.
are currently in progress in our laboratory. 10 (a) P. Kanyong, S. Rawlinson and J. Davis, J. Electroanal.
Chem., 2016, 766, 147–151; (b) G. Amala, J. Saravanan, D. Jin
Yoo, A. R. Kim and G. G. Kumar, New J. Chem., 2017, 41,
Conflicts of interest 4022–4030.
11 (a) H. Yao, N. Li, S. Xu, J.-Z. Xu, J.-J. Zhu and H.-Y. Chen,
The authors declare no conflict of interest.
Biosens. Bioelectron., 2005, 21, 372–377; (b) S. Zheng, B. Li,
Y. Tang, Q. Li, H. Xue and H. Pang, Nanoscale, 2018, 10,
Acknowledgements 13270–13276.
12 S. Cao, B. Li, R. Zhu and H. Pang, Chem. Eng. J., 2019, 355,
We gratefully acknowledge the financial support from the DST 602–623.
Indo-Italian Joint Project [No. INT/Italy/P-15/2016 (SP)]. The 13 (a) X. Qin, H. Wang, Z. Miao, J. Li and Q. Chen, Talanta,
authors gratefully acknowledge the Transdisciplinary Research 2015, 139, 56–61; (b) P. Lu, J. Yu, Y. Lei, S. Lu, C. Wang,
Grant from VIT and VIT-SIF for providing the instrumentation D. Liu and Q. Guo, Sens. Actuators, B, 2015, 208, 90–98.
facilities. The authors would like to thank Dr. Annamalai Senthil 14 (a) J. Chang, H. Li, T. Hou, W. Duan and F. Li, Biosens.
Kumar (VIT) for the helpful discussion on the sensing mechanism. Bioelectron., 2018, 104, 152–157; (b) W. Yang, X. Li, Y. Li,
R. Zhu and H. Pang, Adv. Mater., 2018, 1804740, 1–35.
References 15 S. Hazra, H. Joshi, B. K. Ghosh, A. Ahmed, T. Gibson,
P. Millner and N. N. Ghosh, RSC Adv., 2015, 5, 34390–34397.
1 Z. Song, R. T. K. Kwok, D. Ding, H. Nie, J. W. Y. Lam, B. Liu 16 (a) L. Fan, Q. Zhang, K. Wang, F. Li and L. Niu, J. Mater.
and B. Z. Tang, Chem. Commun., 2016, 52, 10076–10079. Chem., 2012, 22, 6165–6170; (b) J. Losada, P. Garcı́a-Armada,

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019 New J. Chem., 2019, 43, 8539--8550 | 8549
 View Article Online

Paper NJC

V. Robles, Á. M. Martı́nez, C. M. Casado and B. Alonso, New 37 K. Senthilkumar, M. Pizzotti, K. Thirumoorthy, G. Di Carlo,
J. Chem., 2011, 35, 2187–2195. S. Righetto, A. Orbelli Biroli, M. Haukka and N. Palanisami,
17 G.-C. Zhao, M.-Q. Xu and Q. Zhang, Electrochem. Commun., J. Phys. Chem. C, 2016, 120, 20277–20287.
2008, 10, 1924–1926. 38 U. M. Rabie, Spectrochim. Acta, Part A, 2009, 74, 746–752.
18 (a) N. Sun, L. Guan, Z. Shi, N. Li, Z. Gu, Z. Zhu, M. Li and 39 M. Gopalakrishnan and N. Palanisami, RSC Adv., 2016, 6,
Y. Shao, Anal. Chem., 2006, 78, 6050–6057; (b) W. Oungpipat, 1760–1768.
P. W. Alexander and P. Southwell-Keely, Anal. Chim. Acta, 1995, 40 M. F. Zaki, Braz. J. Phys., 2008, 38, 558–562.
309, 35–45. 41 S. Hassanien and A. A. Akl, Superlattices Microstruct., 2016,
19 M. Mattoussi, F. Matoussi and N. Raouafi, Sens. Actuators, B, 89, 153–169.
2018, 274, 412–418. 42 (a) C. Kiran Kumar, R. Trivedi, L. Giribabu, S. Niveditha,
Published on 02 May 2019. Downloaded by Idaho State University on 7/17/2019 6:59:57 PM.

20 Y. Yang and S. Mu, Biosens. Bioelectron., 2005, 21, 74–78. K. Bhanuprakash and B. Sridhar, J. Organomet. Chem., 2015,
21 R. Hu, J. L. Maldonado, M. Rodriguez, C. Deng, C. K. W. Jim, 780, 20–29; (b) H. Xu, Y. Yue, H. Wang, L. Chen, Y. Hao and
J. W. Y. Lam, M. M. F. Yuen, G. Ramos-Ortiz and B. Z. Tang, B. Xu, J. Lumin., 2012, 132, 919–923.
J. Mater. Chem., 2012, 22, 232–240. 43 R. Prasath and P. Bhavana, J. Organomet. Chem., 2015, 794,
22 Q. Zeng, Z. Li, Y. Dong, C. Di, A. Qin, Y. Hong, L. Ji, Z. Zhu, 181–187.
C. K. W. Jim, G. Yu, Q. Li, Z. Li, Y. Liu, J. Qin and B. Z. Tang, 44 (a) K. Senthilkumar, K. Thirumoorthy, C. Dragonetti,
Chem. Commun., 2007, 70–72. D. Marinotto, S. Righetto, A. Colombo, M. Haukka and
23 X. Y. Shen, Y. J. Wang, E. Zhao, W. Z. Yuan, Y. Liu, P. Lu, N. Palanisami, Dalton Trans., 2016, 45, 11939–11943;
A. Qin, Y. Ma, J. Z. Sun and B. Z. Tang, J. Phys. Chem. C, (b) R. Andreu, M. A. Cerdán, S. Franco, J. Garı́n,
2013, 117, 7334–7347. A. B. Marco, J. Orduna, D. Palomas, B. Villacampa,
24 A. Wang, R. Fan, Y. Dong, Y. Song, Y. Zhou, J. Zheng, X. Du, R. Alicante and M. Allain, Org. Lett., 2008, 10, 4963–4966.
K. Xing and Y. Yang, ACS Appl. Mater. Interfaces, 2017, 9, 45 (a) P. Liu, B. Jin and F. Cheng, J. Electroanal. Chem., 2007,
15744–15757. 603, 269–274; (b) M. Zamora, S. Bruña, B. Alonso and
25 (a) R. T. K. Kwok, C. W. T. Leung, J. W. Y. Lam and B. Z. I. Cuadrado, Macromolecules, 2011, 44, 7994–8007.
Tang, Chem. Soc. Rev., 2015, 44, 4228–4238; (b) M. X. 46 (a) W. C. (Ina) du Plessis, J. J. C. Erasmus, G. J. Lamprecht,
Gao, C. F. Liu, Z. L. Wu, Q. L. Zeng, X. X. Yang, W. B. Wu, J. Conradie, T. S. Cameron, M. A. S. Aquino and J. C. Swarts,
Y. F. Lia and C. Z. Huang, Chem. Commun., 2013, 49, Can. J. Chem., 1999, 77, 378–386; (b) S.-H. Hsiao and K.-H.
8015–8017. Lin, High Perform. Polym., 2016, 29, 544–555.
26 H. Maeda, Y. Fukuyasu, S. Yoshida, M. Fukuda, K. Saeki, 47 R. Balasaravanan, V. Sadhasivam, G. Sivaraman and A. Siva,
H. Matsuno, Y. Yamauchi, K. Yoshida, K. Hirata and Asian J. Org. Chem., 2016, 5, 399–410.
K. Miyamoto, Angew. Chem., Int. Ed., 2004, 43, 2389–2391. 48 R. M. F. Batista, S. P. G. Costa, M. Belsley and M. M. M.
27 F. Hu, Y. Huang, G. Zhang, R. Zhao and D. Zhang, Tetra- Raposo, Tetrahedron, 2007, 63, 9842–9849.
hedron Lett., 2014, 55, 1471–1474. 49 Z. Czyżnikowska, J. Kurzawa, R. Zaleśny, P. Lipkowski and
28 Z. Zhang, R. T. K. Kwok, Y. Yu, B. Z. Tang and K. M. Ng, ACS W. Bartkowiak, Chem. Phys. Lett., 2009, 480, 37–40.
Appl. Mater. Interfaces, 2017, 9, 38153–38158. 50 W. Z. Yuan, Y. Gong, S. Chen, X. Y. Shen, J. W. Y. Lam, P. Lu,
29 R. Zhang, Z. Wang, Y. Wu, H. Fu and J. Yao, Org. Lett., 2008, Y. Lu, Z. Wang, R. Hu, N. Xie, H. S. Kwok, Y. Zhang, J. Z. Sun
10, 3065–3068. and B. Z. Tang, Chem. Mater., 2012, 24, 1518–1528.
30 D. Zhang, L. Zhu, H. Li and J. Su, Front. Chem. China, 2010, 51 A. M. Brouwer, Pure Appl. Chem., 2011, 83, 2213.
5, 241–246. 52 Z. Zhao, J. W. Y. Lam and B. Z. Tang, Curr. Org. Chem., 2010,
31 V. Hardouin Duparc and F. Schaper, Organometallics, 2017, 14, 2109–2132.
36, 3053–3060. 53 M. Shyamal, S. Maity, A. Maity, R. Maity, S. Roy and
32 Y. Liu, J. Yuan, Z.-F. Wang, S.-H. Zeng, M.-Y. Gao, M.-L. A. Misra, Sens. Actuators, B, 2018, 263, 347–359.
Ruan, J. Chen and G.-A. Yu, Org. Biomol. Chem., 2017, 15, 54 C.-S. Chu, M.-W. Hsieh and Z.-R. Su, Opt. Mater. Express,
5805–5810. 2016, 6, 759–766.
33 Y.-C. Shi, C.-X. Sui, H.-J. Cheng and B.-B. Zhu, J. Chem. 55 L. Shang and S. Dong, Anal. Chem., 2009, 81, 1465–1470.
Crystallogr., 2007, 37, 407–413. 56 (a) M. P. G. Armada, J. Losada, I. Cuadrado, B. Alonso,
34 Q. Zhang, W.-L. Song, A. M. Showkot Hossain, Z.-D. Liu, B. González, E. Ramı́rez-Oliva and C. M. Casado, Sens. Actua-
G.-J. Hu, Y.-P. Tian, J.-Y. Wu, B.-K. Jin, H.-P. Zhou, J.-X. Yang tors, B, 2003, 88, 190–197; (b) A. Rabti, N. Raouafi and
and S.-Y. Zhang, Dalton Trans., 2011, 40, 3510–3516. A. Merkoçi, Carbon, 2016, 108, 481–514; (c) M. Honda,
35 M. Devendiran, K. K. Kumar and S. S. Narayanan, T. Kodera and H. Kita, Electrochim. Acta, 1986, 31, 377–383;
J. Electroanal. Chem., 2017, 802, 78–88. (d) C. M. Welch, C. E. Banks, A. O. Simm and R. G. Compton,
36 B. Fábián, A. Csámpai, T. Z. Nagy, M. Czugler and P. Sohár, Anal. Bioanal. Chem., 2005, 382, 12–21.
J. Organomet. Chem., 2009, 694, 3732–3741. 57 C. Ni and J. Hu, Chem. Soc. Rev., 2016, 45, 5441–5454.

8550 | New J. Chem., 2019, 43, 8539--8550 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019