Article

pubs.acs.org/JPCB

The Prospect of Salophen in Fluorescence Lifetime Sensing of Al3+

Tuhin Khan,* Shefali Vaidya, Darshan S. Mhatre, and Anindya Datta*
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India
*
S Supporting Information

ABSTRACT: We have assessed the potential of salophen, a tetradentate

Schiff base, in fluorescence sensing of Al3+ ions. While performing this
investigation, we have noticed conflicting literature reports on the
fluorescence spectral maximum and quantum yield of salophen. So, the
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compound has been purified by repeated crystallization. Fluorescence

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studies have been performed on samples in which the absorption and

excitation spectra are completely superimposable. The purified compound
exhibits a feeble fluorescence at 545 nm, associated with an ultrafast
fluorescence decay. This is rationalized by excited state proton transfer and
torsional motions within the molecule, which provide efficient nonradiative
channels of deactivation of its excited state. The fluorescence quantum yield
increases upon complexation of salophen with Zn2+ as well as Al3+. The
increase is significantly more upon complexation with Al3+. However,
fluorescence maxima are similar for the two complexes. This indicates that
fluorescence intensity may not be a good parameter for Al3+ sensing by salophen, in the presence of a large excess of Zn2+. This
problem can be circumvented if fluorescence lifetime is used as the sensing parameter, as the lifetime of the Al3+ complex is in the
nanosecond time regime while that of the Zn2+ complex is in tens of picoseconds. The significant difference in the fluorescence
quantum yield and lifetime between the two complexes is explained as follows: the Al3+ complex is monomeric, but the Zn2+
complex is dimeric. Quantum chemical calculations indicate a higher density of states near the locally excited state for the dimeric
complex. This may lead to more efficient nonradiative pathways.

T he photophysics of inorganic metal complexes has been

an active field of research for several decades and has
given rise to various applications in artificial photosynthesis,
aluminum could be a neurotoxin in Alzheimer’s disease,
Parkinson disease, etc.13 It is known to inhibit plant growth
in acidic soil, which makes up almost 40% of cultivable land.14 Why they have
photodynamic therapy, biological labeling etc. Fluorescence Al3+ is highly reactive due to its small size and high charge. chosen
Fluorescence
sensing of metal ions is one such application that has received Consequently, it can act as a competitive binder to essential detection of Al+3
considerable attention. This application builds upon the metal ions with similar characteristics, e.g., Ca2+, Mg2+, and
modulation of fluorescence intensity or lifetime of ligands Fe3+.15,16 Unlike many other metal ions, detection of Al3+ is not
upon complexation with metal ions.1 Selectivity and specificity straightforward. Because of its high hydration energy, it readily
are major issues that need to be considered for design of such takes up water and reacts with it to form insoluble Al(OH)3. It
ligands for metal ion sensing. Schiff bases constitute one of the lacks well-defined spectroscopic characteristics like charge
most widely studied classes of ligands in this context, due to transfer and does not form coordination complexes with
their ability to coordinate with a wide range of ions in various most ligands. In recent times, these difficulties have been
oxidation states.2 Their synthesis and chemical modification can surmounted to design several fluorescence sensors of Al3+.17−20
be achieved with relative ease, providing a means for Lee et al. have demonstrated the potential of salophen as a
manipulation of the HOMO−LUMO gap.3,4 Salen (N,N′- turn−on fluorescence sensor of Al3+ ion.21 More recently,
bis(salicylidene)ethylenediamine) and salophen (N,N′-bis- Barboza et al. have reported a decrease in fluorescence quantum
(salicylidene)-o-phenyldiamine) are typical representatives of yield and lifetime of salophen with Zn2+.22 These two papers
this class of ligands. Metal complexes of salen/salophen find report contradictory values of fluorescence maximum (λems) and
application in catalysis, supramolecular chemistry,5 medicine, quantum yield (ϕf) of free salophen. While Barboza et al. have
DNA intercalation,6 organic light emitting diode (OLED),7 reported a strong emission with λems = 450 nm, Lee et al. and
electronics,8 sensing,9 and nonlinear optics (NLO).10 Kotova et al.23 have reported a feeble emission with λems = ca.
In the present study, our focus is on the complex of Salophen 525 nm. This conflict between the two literature reports needs
with Al3+ and Zn2+ ions. Aluminum is the most abundant metal to be resolved. Moreover, Zn2+ is known to form emissive
in the earth’s crust (8.3%) and third most abundant element
after oxygen and silicon. It has no known physiological role, but Received: June 10, 2016
an average human consumes 3−10 mg of the metal every day, Revised: August 6, 2016
due to its high abundance.11,12 It has been proposed that Published: September 7, 2016

© 2016 American Chemical Society 10319 DOI: 10.1021/acs.jpcb.6b05854

J. Phys. Chem. B 2016, 120, 10319−10326
The Journal of Physical Chemistry B Article

complexes with many ligands.24,25 If the fluorescence of Scheme 1. Reaction Scheme of Synthesis of Salophen and Its
salophen is indeed affected by Zn2+, then this could pose a Metal Complex
serious hindrance to sensing of Al3+ by this Schiff base in
solutions where Zn2+ is also present. Notably, zinc is the second
most abundant d-block element in living organisms.26,27 The
human body typically contains 2−3 g of zinc.28 With this
background, we have synthesized salophen, purified it by
repeated crystallization, and performed steady state and time-
resolved fluorescence studies on the free ligand as well as the
complexes with Zn2+ and Al3+.
Before discussing our results, we present a brief overview of
the photophysics of Schiff base compounds, which needs to be
referred to during the rationalization of time-resolved
spectroscopic data. The enol form of the Schiff base is
predominant in solid and solution phase. The locally excited
state formed upon π−π* transition of this form undergoes an
ultrafast twist (torsional motion) and proton transfer in the
time frame of ∼100 fs. The twisted enol form returns to the
ground state via nonradiative pathway through a conical
intersection. The cis-keto form formed as a result of excited
state proton transfer emits at ∼550 nm with a lifetime of ∼10
ps. The cis-keto form further undergoes cis−trans isomerization
to form a long-lived (∼ ms) trans photoproduct.29−31 Upon
complexation, the twisting about the C−C bond is expected to
be hindered significantly. This is likely to bring about an methanol and diethyl ether over 2−3 days. The fine yellow
enhancement in fluorescence intensity and lifetime. The single crystal thus formed was used for XRD and 1H NMR
absence of proton transfer can also be expected to affect the study.
photophysics of salophen in its metal ion complex. We have Characterization of Synthesized Compounds. 1H
sought to understand the interplay of these processes in the NMR studies of SalH2 was carried out in CDCl3 whereas
complexed ligand. SalZn and SalAl+ were carried out in DMSO-d6 in Bruker 400

■ MATERIALS AND METHODS

Synthesis of Salophen and Its Complexes. All chemicals
MHz NMR spectrometer (Figure S1). An ESI−MS study was
carried out with a Bruker maXis Impact mass spectrometer. A
Rigaku Saturn CCD diffractometer, with a graphite mono-
were used without further purification unless mentioned chromator (λ = 0.71073°) and Rigaku Crystal Clear-SM Expert
otherwise. Solvents were of spectroscopic grade. In order to 2.1 software, was used to collect the X-ray data. The structure
synthesize salophen (SalH2), an ethanolic solution of 2 mL of was solved by direct methods and was refined by least-squares
salicyaldehyde (SD Fine Chemicals, Mumbai, India) was added methods on F2 with the SHELXTL package. All non-hydrogen
dropwise with constant stirring at room temperature to 25 mL atoms were refined anisotropically.
of an ethanolic solution of 1 g of 1,2-phenylenediamine (Sigma- Steady State and Time-Resolved Fluorescence Spec-
Aldrich, USA).32 The mole ratio in the final mixture was 2:1 troscopy. UV−visible absorption and emission studies were
(Scheme 1). A bright yellow precipitate of SalH2 was formed in performed on a JASCO V-530 spectrometer and a Varian Cary
about 5 min. The reaction mixture was further stirred for 3−4 Eclipse spectrofluorimeter, respectively. For the fluorescence
h. The precipitate was filtered under suction and repeatedly study, band-pass of 5 nm was used for both excitation and
washed with cold ethanol and diethyl ether. The solid dry mass emission. Fluorescence quantum yield (ϕf) was measured using
was further air-dried for 1−2 days. Finally, it was purified by Coumarin 30 as reference (ϕf = 0.307 in methanol) (additional
repeated crystallization from a hot ethanolic solution. The fine details in the Supporting Infomration).34
crystals formed thereafter were washed with ditheyl ether and The nanosecond lifetime was measured using time correlated
air-dried. These crystals were used for all further studies. single photon counting (TCSPC) spectrometer from IBH
Zn(salophen) (SalZn) was synthesized by the following Horiba Jobin Yvon (FluoroCube). The sample was excited with
procedure: To an ethanolic solution of 100 mg of crystallized a 375 nm diode laser (Horiba NanoLED) with a repetition rate
salophen was added 70 mg of Zn(OAC)2·2H2O (Merck, USA) of 1 MHz. The decay was collected at magic angle (54.7°)
in ethanol dropwise, to maintain a mole ratio of 1:1.32 The polarization with respect to vertically polarized excitation light.
yellow precipitate thus formed was further stirred for 3−4 h, The full width at half-maximum (FWHM) of the instrument
followed by filtration and washing with cold ethanol and diethyl response function (IRF) was approximately 300 ps. The decays
ether. For the synthesis of Al(salophen) (SalAl+), to a were fitted to single exponential function by iterative
methanolic solution of 100 mg of crystallized salophen was reconvolution using IBH DAS 6.2 software.
added 120 mg of Al(NO3)3·9H2O (Merck, USA) in methanol The femtosecond optical gating (FOG) setup has been
dropwise, in order to maintain a mole ratio of 1:1.33 The described elsewhere.35 A detailed description has been provided
resultant yellow solution of the complex was stirred for 3−4 h in the Supporting Infomration. SalH2 was excited at 385 nm
followed by filtration and drying under reduced pressure. The while SalZn, SalAl+, and Sal2− were excited at 400 nm. A magic
solid mass was further washed with dicholoromethane and then angle polarization was maintained to eliminate rotational
decanted and dried under reduced pressure. The crude complex anisotropy. The minimum possible laser power and integration
was then crystallized through a slow diffusion method with time were used in order to avoid photodegrdation of the
10320 DOI: 10.1021/acs.jpcb.6b05854
J. Phys. Chem. B 2016, 120, 10319−10326
The Journal of Physical Chemistry B Article

samples. No concentration dependence was observed in the

kinetic profiles. The decay traces were fitted to a linear sum of
three exponentials with iterative reconvolution of a Gaussian
function of FWHM = 275 fs, using Igor Pro 6.3 platform.
For the study of mixture of zinc and aluminum ion to a total
concentration of 50 μM salophen in acetonitrile mixture of
Zn2+ and Al3+ added with final concentration of Zn2+ and Al3+
being 20 μM and 10 μM respectively. A control experiment was
performed with individual salts at the same concentration. For
both steady state and time-resolved measurement an excitation
wavelength of 375 nm is used and 500 nm as emission
wavelength is used for lifetime measurement. Aluminum salt
was dried under desiccator for 3−4 days.
Quantum Chemical Calculations. Computational calcu-
lation was performed using Gaussian 09 package whereas
GaussView05 was used for drawing and visualization purpose.36
Density functional theory (DFT) calculations were carried out
at the B3LYP level of theory with 6-31G(d) as the basis. The
excited state energy was calculated with time-dependent DFT.
Solvent effect (methanol) was taken care of by using the
polarization continuum model. During geometry optimization,
a frequency calculation was also carried out to make sure that
the structure is at minima.

■ RESULTS AND DISCUSSION

Salophen (SalH2) has an absorption maximum at 330 nm, with
Figure 1. Absorption (blue solid line), emission (red solid line), and
excitation (red circles) spectra of (A) as synthesized/as received SalH2,
(B) SalH2 crystallized once, (C) SalH2 crystallized thrice, and (D)
a molar absorption coefficient of 17000 M−1cm−1 and a filtrate of SalH2 crystallization process in acetonitrile. λex and λem are
shoulder at 370 nm. A very weak band is observed at 450 nm in the excitation and emission wavelength for the corresponding emission
polar solvents like acetonitrile and methanol, but not in and excitation spectra. The excitation and emission spectra are peak
nonpolar solvents like n-heptane and toluene (Figure S2). This normalized. The absorption spectra are normalized at the lowest
weak band can be assigned to the polar cis-monoketo form.37,38 energy peak.
The crude reaction product, as well as the as received sample
from Sigma−Aldrich, exhibits a strong 460 nm emission in the impurity does not absorb wavelengths longer than 350−360
acetonitrile, when excited at the absorption maximum. This is nm. So, excitation wavelengths of 370−385 nm have been used
in agreement with some earlier reports.22,39−41 However, the for all our studies discussed below, in order to ensure selective
excitation spectra of the crude as synthesized/as received excitation of salophen, even if the impurity is present in traces.
salophen recorded with λem = 460 nm are very different from Besides, the choice of this excitation wavelength allows us to
the corresponding absorption spectra (Figure 1A). So, it avoid excitation of minute amounts of salicylaldehyde (λabs =
appears that the 460 nm emission arises from a highly 320 nm) that may be present in solutions of salophen. It may
fluorescent impurity. Upon repeated crystallization, the be noted here that the absorption spectrum as well as the
signature of the impurity becomes negligible. spectral and temporal characteristics of fluorescence of the
A feeble emission (ϕf = ca. 1.4 × 10−4 in acetonitrile) with impurity suggests that it is likely to consist of one or more
λem = 545 nm (Figure 1B,C) is obtained, using λex = 370 nm. benzimidazole derivatives42,43 which are reported to form as
This is in agreement with the position of the emission maxima major products44 of the reaction between the same reactants at
reported by Lee et al. in solution and Kotova et al. in solid different reaction condition. It is worth noting that N,N′-
state.21,23 For λex = 320 nm, the impurity emission is observed bis(salicylidene)-p-phenylenediamine and salicylideneaniline
for once−crystallized salophen, albeit to a lesser extent (Figure which falls in the same family of Schiff base emits in the
1B). For thrice−crystallized salophen, the excitation spectrum region of 550 nm.30,37
for λem = 560 nm is superimposable with the absorption Steady state spectra undergo remarkable changes upon
spectrum (Figure 1C). The emission peak for 10 μM and 90 complexation with Zn2+ as well as with Al3+ (Figure 2A−C).
μM solutions of salophen are found to be identical (Figure S3). The absorption spectra of the complexes are red-shifted to 390
Hence, the possibility of aggregation of salophen in solution is nm (Figure 2, parts B and C), which is close to the absorption
ruled out since the solubility of salophen in acetonitrile is >30 maximum of salophen anion, Sal2−, prepared by treating SalH2
mM. Interestingly, the filtrate obtained during crystallization with the non-nucleophilic base NaH in tetrahydofuran (THF)
exhibits a strong fluorescence at 460 nm. The absorption (Figure 2D).45 Notably, there is a strong band in the 420−450
spectrum of the filtrate is superimposable with the excitation nm region for the complexes, where the absorption of the cis-
spectrum of the highly emissive impurity (Figure 1D). Thus, keto form of SalH2 occurs. This band is present, albeit to a very
the filtrate is found to be enriched in the impurity. The small extent, in the absorption spectrum of SalH2 in methanol
fluorescence decay of the highly emissive impurity is single (Figure S2). The absorption band of the enol form is absent in
exponential, with a lifetime of 3.6 ns in acetonitrile (Figure S4), the complexes, as there is no enolic proton. Consequently,
while the fluorescence of purified salophen decays within tens there is no possibility of ESIPT unlike in the free ligand. It may
of picoseconds (vide inf ra). Excitation spectra of the crude be mentioned here that the absorption is predominantly due to
product, monitored with λem = 450 nm (Figure 1), indicate that intraligand π−π* transitions.46 The emission maximum of the
10321 DOI: 10.1021/acs.jpcb.6b05854
J. Phys. Chem. B 2016, 120, 10319−10326
The Journal of Physical Chemistry B Article

is encouraging from the point of view of fluorescence sensing.

However, a difficulty arises due to the almost identical position
of the emission maxima of the two complexes. Large excess of
Zn2+ can interfere with the Al3+ sensing ability of SalH2. Since
zinc is a more abundant metal than aluminum in human body,
this difficulty could be nontrivial during in vivo detection of
Al3+.
Time resolved fluorescence studies have been performed in
order to understand how fluorescence lifetimes are affected
upon complexation. The motivation for this study is 2-fold. If
the lifetimes are significantly different in the two complexes,
then they can be used as an effective parameter for selective
sensing of one of the metal ions. Besides, these studies provide
an insight into the effect of complexation on the excited state
dynamics of fluorophore. The fluorescence of SalH2 decays
within 60 ps while that for Sal2− decays within 40 ps. The
ultrafast decay (Figure 3A) can be attributed to efficient

Figure 2. Absorption (blue), emission (red solid line), and excitation

(red circles) spectra of (A) SalH2, (B) SalZn, (C) SalAl+ in acetonitrile
and (D) Salophen anion (Sal2−) in THF. λex and λem are the excitation
and emission wavelength for the corresponding emission and
excitation spectra. The excitation and emission spectra are peak
normalized. The absorption spectra are normalized at the lowest
energy peak.

zinc complex of salophen (SalZn) occurs at 505 nm (Figure

2B). Its fluorescence quantum yield is greater than that of SalH2
by an order of magnitude (ϕf = 1.1 × 10−3 in acetonitrile). The
aluminum complex, SalAl+, exhibits an emission with maximum
at 495 nm (Figure 2C) and ϕf = 7.4 × 10−2 in acetonitrile
(Table 1). This 500 fold enhancement of emission with Al3+ is

Table 1. Steady State Photophysical Parameters of Salophen,

Its Complexes (in ACN), and Salophen Anion (in THF)
sample λabs (nm) λems (nm) ϕf
SalH2 330 545 ∼1.4 × 10−4
SalZn 390 505 1.1 × 10−3
SalAl+ 385 495 7.4 × 10−2
Sal2− 380 490 − Figure 3. Fluorescence decay profile of SalH2, SalZn, and SalAl+, at the
respective emission maxima, recorded by (A) the FOG technique
in line with earlier reports of SalH2 being a turn on fluorescent (normalized) and by (B) the TCSPC technique. Additionally, the
sensor for Al3+.21 The position of the emission maximum is fluorescence decay of Sal2− has been shown in part A and that of SalH2
close to that of Sal2− in both the cases (480 nm, Figure 2D). crystal, superimposed with SalH2 in ACN, has been shown in part B.
The slight red shifts are likely to be due to change in energy
levels complexation with the metal ions. The increase in ϕf due
to complexation is explained as follows: The low quantum yield nonradiative deactivation of the excited state due to torsional
of Schiff bases has been assigned to the flexible structure of motions about the bonds, as reported for other Schiff bases.30
these molecules, which facilitate segmental motion like The faster decay in Sal2− may be attributed to a more flexible
photoisomerization about the CN bond and rotation about structure than that of SalH2, due to the lack of the phenolic
the C−C single bond. Rigidification of the molecule, by hydrogen atoms and consequent intramolecular hydrogen
complexation with metal ions, leads to the suppression of such bonding. It may be noted that in earlier studies, the longest
segmental motion and hence cuts down the associated component of a very similar Schiff base salicyledeneaniline, has
nonradiative channels of deactivation of the excited state, been attributed to the cis-keto form. The shortest component
leading to an increase in fluorescence quantum yield and has been assigned to the enol form and the intermediate
lifetime. The significantly greater degree of enhancement of component has been assigned to the emission from vibration-
fluorescence intensity upon complexation of salophen with Al3+ ally excited cis-keto form.30
10322 DOI: 10.1021/acs.jpcb.6b05854
J. Phys. Chem. B 2016, 120, 10319−10326
The Journal of Physical Chemistry B Article

The fluorescence decay becomes slower upon complexation respectively). In this experiment, we find that in steady state
with Zn2+, indicating the suppression of nonradiative processes emission spectra it is difficult to identify either of the two metal-
that occur prior to complexation. The decays are multi- complexes (Figure S5). But in time-resolved measurement, a
exponential in both the cases (Table 2). The longest lifetime clear signature of the Al3+ of nanosecond lifetime is observed
(Figure 4). The associated lifetime is 1.6 ns, which is the same
Table 2. Kinetic Parameters of Salophen, Its Complexes, and
anion
FOG TCSPC
sample λex/λem (nm) τ (ps) a
λex/λem (nm) τ (ns)
SalH2 385/550 0.2 (0.26) 375/550 <0.1
ACN 5.0 (0.21) ACN
14.8 (0.53)
SalZn 400/510 0.6 (0.38) 375/510 <0.1
ACN 5.4 (0.15) ACN
34.4 (0.46)
SalAl+ 400/490 1.2 (0.13) 375/490 1.6
MeOH 14.4 (0.05) ACN
∼ns (0.82)
Sal2− 400/490 0.4 (0.39) − − Figure 4. Fluorescence decay profiles, monitored at λem = 500 nm, of a
THF 2.6 (0.33) mixture of Zn2+ and Al3+ salts (blue) and control solutions containing
9.2 (0.28) only Al3+ (green) and only Zn2+ (black, superimposable with the IRF)
a
The numbers in the brackets denote fractional amplitudes. salts in acetonitrile. λex = 375 nm.

increases from 15 ps in SalH2 to 35 ps in SalZn (Figure 3A, as that observed for isolated SalAl+. Moreover, an ultrafast
Table 2). This increase in lifetime reflects the hindrance to the component (<100 ps) corresponding to the zinc complex is
nonradiative channels associated with torsional motion of the also observed as an initial fast decay. Thus, it is demonstrated
segments of the molecule. It rationalizes the increase in that lifetime measurement can not only be used for
fluorescence quantum yield by an order of magnitude upon identification of Al3+ ion in mixture of Zn2+ and Al3+ but also
complexation with Zn2+. However, the observed decay of for simultaneous detection of Zn2+ in the mixture.
fluorescence of SalH2 as well as SalZn are much faster than The question that now remains to be addressed is why the
those reported recently, confirming that the species studied in enhancement in fluorescence quantum yield and lifetime are so
those reports were due to a highly emissive impurity and not different between SalAl+ and SalZn. A tentative explanation
salophen itself.22 may be proposed in the light of monomer−dimer equilibrium.
Complexation with Al3+ is associated with a fast decay with Such equilibria have been reported in literature for Zn−
very small contribution, along with a major component that is complexes of salen and some other Schiff bases.47−49 According
significantly slower, to the extent that the decay is not complete to DFT calculations, the equilibrium is strongly favored toward
in the FOG time scale (Figure 3A). The decay is therefore the dimer, (SalZn)2 over the monomer, SalZn.50 Strong Lewis
recorded using TCSPC, which yields a single component of 1.6 bases, e.g., pyridine (Py) reportedly disrupt (SalZn)2 by taking
ns in acetonitrile (Figure 3B and Table 2). The significant up the axial position and forming SalZnPy.51,52 In our
increase in lifetime is in line with the increase in fluorescence experiment, the fluorescence decay of SalZn in pyridine (and
quantum yield by more than a couple of orders of magnitude DMSO) has been found to be slower than that in acetonitrile
upon complexation with Al3+ and implies a very efficient (Figure S6). However, it is significantly faster than that of
suppression of the segmental motion of the fluorophore SalAl+. ESI−MS spectra of SalAl+ and SalZn have been
molecule. In fact, the fluorescence decay of SalAl+ in recorded in order to understand if the complexes are
acetonitrile is superimposable with that of SalH2 crystals monomeric or dimeric. A distinct signature of the dimer is
(Figure 3B), indicating that the suppression of nonradiative obtained in case of SalZn in our experiment as well as in ref 50
processes in SalAl+ takes place to a similar extent as in SalH2 while such a signature is absent in case of SalAl+ (Figure S7).
crystal. This leads to an interesting situation. In the presence of Additionally 1:1 stochiometry for SalZn (Figure S8) is
a large excess of Zn2+, the lifetime of SalZn, which is in tens of confirmed from Job’s plot. Single crystals of the SalZn have
picoseconds, is not resolvable by TCSPC experiments, unlike remained elusive as of now. However, the crystal structure of
the nanosecond lifetime of SalAl+. The problem associated with SalAl+ confirms that the Al−complex is monomeric and
fluorescence sensing of Al3+ by SalH2, in the presence of a large octahedral (CCDC 1482138), with two solvent (methanol)
excess of Zn2+, is thus addressed and fluorescence lifetime molecules at the axial positions. The basal plane is occupied by
emerges as a parameter by which Al3+ sensing can be achieved the ligand, which assumes a planar geometry around the central
using salophen. TCSPC, which has become a very commonly atom (Figure S9).
used technique, can be conveniently used for this purpose. In absence of X-ray crystallographic data, we propose, on the
A proof of principle experiment has been performed with a basis of ESI−MS data and existing literature49,50 that
mixture of Zn2+ and Al3+ ion with mole ratio of 2:1 (20 and 10 fluorescence is quenched significantly in the dimeric complex
μM, respectively), in order to test the validity of our of salophen with Zn2+, whereas such quenching does not occur
contention. Control experiments have been performed on in the monomeric Al3+ complex. The mechanism of quenching
two separate solutions of the same concentration of salophen in SalZn is not very clear at this time. Spin−orbit coupling has
containing only Al3+ and only Zn2+ salts (20 and 10 μM, been reported to provide a nonradiative pathway in Zn2+-
10323 DOI: 10.1021/acs.jpcb.6b05854
J. Phys. Chem. B 2016, 120, 10319−10326
The Journal of Physical Chemistry B Article

complexes of porphyrin.53,54 A similar mechanism may operate

in SalZn as well. However, the time scales of intersystem
■ ACKNOWLEDGMENTS
This work is supported by a SERB, DST project of A.D. FIST
crossing (ISC) in coordination complexes do not always support to the Department of Chemistry, IIT Bombay, is
correlate with the value of the spin orbit coupling constant.55 acknowledged gratefully. T.K. and S.V. are grateful to the CSIR
Rather, density of states and structural considerations appear to for research fellowships. Department of Chemistry and IIT
play a more important role.56 In our DFT calculations, the Bombay are thanked for the high performance computing
density of states has been found to be significantly more in the facilities. Also, this paper is dedicated to Professor Dipak
dimeric complex, than in the monomeric form (Figure S10). Kumar Palit in his 60th year.
This could be the reason for a significantly lesser fluorescence
quantum yield and lifetime in SalZn than in SalAl+. ■ REFERENCES

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