Synthesis of a phenylhydrazone-based colorimetric anion sensor with complementary IMP/INH logic functions

Article abstract of DOI:10.1002/cjoc.201200149

A dinitrophenyl hydrazone colorimetric anion sensor (receptor 1) was synthesized and its recognition properties towards various anions were investigated by naked eye observation and spectroscopic methods, namely UV-vis and ¹H NMR titrations in DMSO. The addition of AcO^-, F^- and H₂PO₄^- to receptor 1 resulted in marked red shift of the charge-transfer absorbance band (Δλ=91 nm, 407 nm to 498 nm) concomitant with a 'naked-eye' detectable colour change from yellow to pink. However, both the colour and spectral changes were reversible by the addition of cations (M^II) of 3d^5-10 as well as Cd^II, Hg^II, Mg^II and Ca^II. Subsequently, complementary IMP/INH logic functions based on colour and spectral switching (ON/OFF) were affirmed. The sensor can, thus be utilized as a colorimetric molecular switch modulated by F^-/M^II.

Full text of DOI:10.1002/cjoc.201200149

FULL PAPER
DOI: 10.1002/cjoc.201200149
Synthesis of a Phenylhydrazone-based Colorimetric Anion
Sensor with Complementary IMP/INH Logic Functions
Uahengo, Veikko(韦科)
Xiong, Bi(熊碧)
Zhou, Nana(周娜娜)
Cai, Ping*(蔡苹)
Hu, Kai(胡锴)
Cheng, Gongzhen*(程功臻)
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, China
A dinitrophenyl hydrazone colorimetric anion sensor (receptor 1) was synthesized and its recognition properties
towards various anions were investigated by naked eye observation and spectroscopic methods, namely UV-vis and
1H NMR titrations in DMSO. The addition of AcO－, F－ and H2PO－4 to receptor 1 resulted in marked red shift of
the charge-transfer absorbance band (∆λ＝91 nm, 407 nm to 498 nm) concomitant with a ‘naked-eye’ detectable
colour change from yellow to pink. However, both the colour and spectral changes were reversible by the addition
of cations (MII) of 3d5-10 as well as CdII, HgII, MgII and CaII. Subsequently, complementary IMP/INH logic func-
tions based on colour and spectral switching (ON/OFF) were affirmed. The sensor can, thus be utilized as a colori-
metric molecular switch modulated by F－/MII.
Keywords colorimetric sensor, hydrazone, anion recognition, logic function
Introduction
F－ and H2PO－4 interact with the sensor through the
NH group by means of hydrogen-bonding.[10] The pres-
ence of an excess anion may even cause deprotonation,
resulting in a classical Bronsted acid-base type reac-
tion.[13]
The sensing and the recognition of anions have been
receiving a great deal of attention due to their wide
range of applications in bio-chemical systems, envi-
ronmental processes and molecular switch designs.[1]
Colorimetric sensors are of great interest in practical
applications due to their simplicity in use and they can
provide quantitative signal rapidly, which allows na-
ked-eye detection of anions without resorting to any
spectroscopic instrumentation.[2] Generally, a colorimet-
ric sensor molecule consists of two parts: the anion
binding part (receptor) and the chromophore.[3] The
binding part may be based on various combinations of
amides,[4] urea,[5] pyrroles,[6] thiourea,[7] pyrazoles,[8]
indoles,[9] hydrazones,[10] imidazoles[11] and carba-
zoles[12] because their NH groups are known to interact
with anions. The chromophore part is responsible for
transducing binding induced changes into optical signals
such as colour changes. With the reference to the bind-
ing parts, only a limited number of reports of hydra-
zone-based receptors are available. Among others, hy-
drazone receptors along with indoles and carbazoles and
their derivatives are better hydrogen bond donors and
both are prone to deprotonation at higher anionic guest
concentration.[12f] Hydrazones are characterized by one
or more nitro-groups (NO2), a molecular framework of
electron withdrawing group (EWG), which polarizes the
NH fragment, thereby increasing hydrogen-bond donor
strength. In these cases, highly basic anions like AcO－,
Alternatively, the functional principles of molecular
switches are similar to chemosensors, whereby the in-
troduction of an anion acts as external stimulus in a
molecular system,[14] which triggers the change (chemi-
cal or physical) of components. These changes can be
detected spectrally and/or visually (color changes),
which in turn are used to monitor the operation of the
system. The essential feature of the molecular switches
is their ability to reverse the changes brought by exter-
nal stimulus such as to restore the initial state of the
sensor by means of opposite stimulus. Thus, since the
pioneering work on molecular AND logic gates by de
Silva and coworkers,[14n] other logic functions such as
NAND, OR, XNOR, XOR, NOR, NOT and INHIBIT
logic operations have been explored, and remarkable
progress has been made in the development of molecu-
lar logic gate.[14f-14m] Acknowledgingly, there is a sig-
nificant number of reports elaborating combinatorial
multiple logic functions, based on both Boolean and
non-Boolean[14o-14s] logic systems in the literature, how-
ever, combinatorial molecular systems with comple-
mentary logic functions remain continuously illusive.[15]
In this paper, an anion sensor (receptor 1) based on a
hydrazone moiety was synthesized (Scheme 1). It was
*
E-mail: caipingwhu@163.com
Received February 16, 2012; accepted March 15, 2012; published online XXXX, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200149 or from the quthor.
Chin. J. Chem. 2012, XX, 1—7
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1

Uahengo et al.
FULL PAPER
1
prepared by the condensation of an aldehyde and a hy-
drazine. The results showed that receptor 1 was able to
selectively recognize AcO－, F－ and H2PO－4 through
the formation of a 1∶1 hydrogen-bonding complex,
concomitant with a ‘naked-eye’ detectable colour
change during the recognition. However, the changes
observed during anion recognition can be significantly
reversed by the addition of cations (MII) of 3d5-10 as well
as CdII, HgII, MgII and CaII (nitrate, chloride and per-
chlorate salts) as compared to protic solvents. Subse-
quently, logic operation properties based on anion-
cation as inputs were investigated, and as a result, the
outputs of receptor 1 were in accordance with com-
plementary IMP/INH logic functions.[15]
otherwise. H NMR titrations were performed on molar
ratio solutions of receptor 1 and tetrabytylammonium
(TBA) salts of F－. Reversibility studies were carried-out
using salt cation solutions of Zn(NO3)2, Cu(NO3)2,
Pb(NO3)2, Ni(NO3)2 and CoCl2 (hydrated), which were
all dried prior to use.
Synthesis of receptor 1
2,4-Dinitrophenylhydrazine (50 mg, 0.25 mmol) in
warm phosphoric acid (10 mL) and ethanol (25 mL)
was added to 3,4,5-tris(2,5,8,11-tetraoxatridecan-13-
yloxy)benzaldehyde[16] (180 mg, 0.25 mmol) and heated
to reflux for 6 h. After removing ethanol, water (100 mL)
was added, then extracted with methylene dichloride.
The combined extract in methylene dichloride was
washed with a saturated solution of sodium chloride and
dried over sodium sulfate. After removing methylene
dichloride, the oily deep red compound was obtained.
The oily product was purified in a silica gel column (60
cm) and collected in CCl4∶CHCl3∶CH3OH (2∶2∶1)
mobile phase as an orange red compound (yield 78%,
Experimental
Instruments
1H NMR spectra were acquired on a Varian Mercury
VX-300 MHz spectrometer. UV-vis spectra were re-
corded using a Tu-1901 UV-vis spectrophotometer (1
cm quartz cell). C, H, N elemental analyses were ac-
quired on a Perkin-Elmer 240C analytical instrument.
1
176 mg). H NMR (300 MHz, DMSO-d6) δ: 11.70 (s,
1H, NH), 8.87 (s, 1H, N＝CH), 8.56 (s, 1H, ArHNO2),
8.35 (d, J＝9 Hz, 1H, ArHNO2), 8.14 (d, J＝9.6 Hz, 1H,
ArHNO2), 7.10 (s, 2H, ArH), 2.50—4.30 (m, 57H, OCH2-
CH2O). The UV-Vis spectrum of receptor 1 exhibits a
Reagents
Commercially available solvents and reagents were
used without further purification, and were all of ana-
lytical grades. Deuterated dimethyl sulfoxide (DMSO)-
d6 for 1H NMR was bought from Aldrich. All TBA salts
(F－, Cl－, Br－, I－, AcO－, H2PO－4 ) and other reagents
(including the mobile phase) were purchased from
Sigma-Aldrich and dried in silica gel desiccators before
use. All other reagents, salts were dried before use in a
desiccators containing P2O5 or distilled in reduced
pressure. All UV-vis titrations were performed in 1.0×
－
－
1
1
band at 407 nm (ε＝24 470 dm3•mol •cm ) due to the
π-π* transition. Elemental analysis calcd for C39H56-
N4O19: C 52.9, H 6.4, N 6.3; found C 53.1, H 6.2, N 6.3.
Results and discussion
UV-Vis analysis of receptor 1
The anion binding ability of the receptor 1 was stud-
ied in HPLC grade DMSO by adding standard solutions
of tetrabutylammonium (TBA) salts of AcO－, H2PO－4 ,
F－, Cl－, Br－ and I－ at room temperature. Figure 1
10－ mol•L－ solution of receptor 1 in DMSO except
5
1
the Job plot (1.0×10－ mol•L ) or unless mentioned
－
4
1
Scheme 1 Synthesis of receptor 1
O
O
O
O
O
H3PO4, C2H5OH
H
O
O
O
CHO
+
O2N
N NH2
O
O
100 ℃
O
O
NO2
O
O
O
2
O
O
O
Hd
O
O
O
O
O
O
O
O
O
N
NH
NO2
Ha
NO2
Hd
Hc
O
O
O
Hb
receptor 1
2
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Chin. J. Chem. 2012, XX, 1—7

Synthesis of a Phenylhydrazone-based Colorimetric Anion Sensor
－
－
Figure 1 UV-vis spectral changes of receptor 1 (1.0×10－ mol•L ) in DMSO upon addition of 0—4 equiv. of (a) AcO and (b) F－.
5
1
Inset: titration profile on the band at 407 nm and 498 nm indicating a 1∶1 adduct (a) AcO－-receptor 1 and (b) F－-receptor 1.
(a and b) shows the changes in the UV-vis spectra of
occurring with excess F－. The addition of 0.5 to 1 equiv.
of F－ where the pink colour appears and persists is a
result of hydrogen bonding interaction between F－ and
the NH, whereas excess F－ induces the deprotonation
of receptor 1.[17,18] Meanwhile, the limit of detection
(LOD) of receptor 1 is at 1×106 mol•L－1 at 25 ℃.
Interestingly, the spectral shift and the pink colour
produced by the addition of anions were significantly
reversed by the additions of various cations (MII) of
3d5-10 configuration, as well as CdII, HgII, MgII and CaII
(anhydrous salts) as compared to protic solvent such as
water, where excessive quantities may be required. Fur-
thermore, the addition of ns1 cations (anhydrous salts)
such as Li＋, Na＋, Ka＋ did not generate any significant
change at all, even when different forms (F－, Cl－, I－,
ClO－4 , Br－) were used, except LiCl which could reverse
the changes, the action attributable to the electrostatic
interaction between Li＋ and highly electronegative F－
in the solution. Apart from LiCl, no other forms of lith-
ium halide (F－, I－, Br－) or any other compound ( ClO－4 )
used could revert the change. Moreover, acidic species
such as chloroacetic acid could significantly reverse the
spectral and visual changes when added, presumably
due to acid-base interaction.[13]
receptor 1 at a concentration of 1×10－ mol•L－ upon
addition of AcO－ and F－ respectively. With the grad-
ual addition of any of these anions, the absorbance peak
centered at 407 nm resulting from the π-π* transition of
the 2,4-dinitrophenyl hydrazine, disappeared gradually
accompanied with the formation of a new band centered
at 498 nm, resulting from intermolecular charge transfer
(ICT) between the electron rich NH and the electron
deficient NO2.[17] At the same time, the colour of recep-
tor 1 changed from yellow to pink (Figure 2) which
could be detected with the naked-eye. The spectral
red-shift (∆λ＝91 nm) and the colour change (yellow to
pink) show that there exists strong hydrogen bonding
interactions between receptor 1 and the anions (AcO－
and F－). The presence of a well-defined isosbestic point
at 442 nm indicates the presence of a complex in equi-
librium with receptor 1. The addition of H2PO－4 in-
duced similar changes in UV-vis spectra with spectral
changes induced by F－ and AcO－, but with a relatively
high volume (ESI, Figure S1). However, no significant
spectral responses or colour changes were observed
when adding Cl－, Br－ and I－, even when large amounts
were used (ESI, Figure S2).
5
1
Continuous variation method was used to determine
the stoichiometric ratios of the host (receptor 1) and the
specific guest anion.[10g] The experimental procedures
consisted of preparing series of solutions of host and
guest anions such that the sum of the total concentra-
tions is constant (1×10－ mol•L ), with the molar
fraction continuously varying. The wavelength was
chosen where the absorbance was largest upon host-
guest complexation (498 nm). The difference between
the observed absorbance and the free receptor 1 (498
nm) in each series was plotted against the molar fraction
[x＝[H]/([H]＋[G])].[10b] The Job’s plot indicated the
formation of a 1∶1 complex between receptor 1 and
the three anions (ESI, Figure S3). The statistical data in
the non-linear curve fitting for AcO－ and F－ illustrated
(Figure 1a and 1b insets), correlate to a 1∶1 host-guest
ratio respectively.
－
5
1
Figure 2 Colour change displayed upon addition of anions (A－
＝AcO－, F－ and H2PO－4 ) to receptor 1 at 10 µmol•L－1 and 100
－
1
µmol•L .
In addition, the 1H NMR titrations suggested that the
interaction of F－ with receptor 1 is a two-step process:
(i) the formation of F-HN hydrogen-bond complex at
low F－ concentration and (ii) the deprotonation process
Chin. J. Chem. 2012, XX, 1—7
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3

Uahengo et al.
FULL PAPER
The corresponding binding constants for a 1∶1
host-guest complex were determined from their indi-
vidual spectroscopic UV-vis absorption titration data
(Table 1) at 25 ℃ by using a nonlinear least square
fit[10c] of the absorbance versus the concentration of the
cation added according to the equation:
1H NMR analysis in DMSO and DMSO-d6 solutions
respectively were carried-out. ZnII among other cations
was selected, not only for its environmental friendliness
and excellent bio-system roles, but its d10 configuration
in NMR analysis. The addition of 1 equiv. ZnII as a ni-
trate solution to the host-guest solution (receptor 1＋F－)
saw the disappearance of the pink colour (Figure 3a)
and the restoration of the original yellow colour. The
naked eye observed was reflected spectrally by the dis-
appearance of the peak at 498 nm and the reappearance
of the absorption band at 407 nm (Figure 3b). The
amount of ZnII needed to completely restore receptor 1
suggested that there existed a 2∶1 (F∶Zn) ratio inter-
action between F－ and ZnII, giving rise to 1∶2∶1 (re-
ceptor 1∶F∶MII). This had eventually demonstrated
that ZnII was directly interacting with F－ rather than
with the sensor. Similar behaviours were observed when
other cations were used (ESI, Figure S6). Virtually, re-
versibility studies of receptor 1 had just prompted the
possibility and curiosity of exploring the molecular
logic functions[15] based on colorimetric switch modu-
lated by F－/MII.
A＝A
0＋
(Alim－A
0){C
H
＋C
G＋1/K
a－[(C
H＋C
G＋1/K
a
)2－4C
H
C
]1/2 }
G
2C
H
where A is the intensity of absorbance; A0 is the inten-
sity of absorbance of the host only; Alim is the maximum
intensity of absorbance of host when guest is added; Ka
is the affinity constant of host-guest; CH and CG are the
concentration of the host and guest respectively. The
association constants of receptor 1 towards the anions
are listed in Table 1. Accordingly, the spectral changes
under the same titration conditions, the Ka of receptor 1
for AcO－ should be slightly larger than F－, a trend well
known for hydrazone receptors.[10] The binding affinity
trend displayed by receptor 1 in DMSO was: AcO－≥F－
＞ H2PO－4 >>>>Cl－≈Br－≈I－.
－
Table 1 Association constant (Ka, L•mol ) of receptor 1 with
1
F－, AcO－ and H2PO－4
Aniona
F－
AcO－
Ka
9.63×104
1.05×105
0.17×102
H2PO－4
a The anions were added in their tetrabutylammonium salts.
Despite the remarkable response towards the above-
mentioned anions, receptor 1 displayed mixed results in
acetonitrile solution (CH3CN). In CH3CN, similar
changes were observed for F－ (like in DMSO), despite
a 14 nm hypsochromic shift, however, no significant
change was observed for AcO－ and H2PO－4 (ESI,
Figure S4). Conclusively, the solvent polarity played a
major role in host-guest interactions too.
Reversibility studies
－
Figure 3 (a) Color changes of receptor 1 (1.0×10－ mol•L )
in DMSO. Left to right: in the absence of ions, in the presence of
4 equiv. of F－ and in the presence of 4 equiv. of F－ along with 2
equiv. of M (M＝MII (3d5-10), CdII, HgII, MgII and CaII). (b) The
reversal of the UV-vis spectral pattern of receptor 1＋4 equiv. of
F－ upon concomitant addition of 2 equiv. ZnII ions.
5
1
Ideally, the recovery of the deprotonated receptor 1
should be possible based on the deprotonation mecha-
nisms. Hydrogen bonding donor solvents such as water
and methanol would compete with anion guest anions
for receptor sites, the N—H.[5b,19] However, in this case
reversibility studies indicated that water could hardly
fully restore the deprotonated receptor 1 (ESI, Figure S5)
even when large amount was used, however, there was a
remarkable response when several cations (ZnII, CuII,
PbII, NiII, CoII) were used (ESI, Figure S6). More
cations were studied, but only few are presented in the
work due to similarity in behaviours (reversibility) to
those shown here.
Logic operation studies with F－ and M as inputs
Logic operation capabilities of receptor 1 were stud-
ied based on its reversibility studies (Figure 3b). The
addition of appropriate combinations of F－ and ZnII as
inputs, produced the outputs (Figure 4a) which are in
accordance with complimentary IMP/INH logic func-
tions.[15a,15c,15f] The process is initiated (ON) by the ad-
dition of input 1 (AcO－, F－, H2PO－4 ) and reversed
In order to study and further elucidate the reversibil-
ity properties of a deprotonated receptor 1, UV-vis and
4
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Chin. J. Chem. 2012, XX, 1—7

Synthesis of a Phenylhydrazone-based Colorimetric Anion Sensor
(OFF) by the input 2 (ZnII, CuII, PbII, NiII, CoII, CrII,
MnII, FeII, MgII, CaII). The spectral changes at 498 nm
upon the addition of inputs are complementary to an
INHIBIT (INH) logic gate, while at 407 nm are in ac-
cordance with an IMPLICATION (IMP) logic gate.
Furthermore, no visual observation was detected after 2
equiv. of ZnII was added to receptor 1, except a slight
hyperchromic shift at 407 nm (ESI, Figure S7). The ad-
dition of 5 equiv. of F－ to the solution of receptor 1＋2
equiv. ZnII resulted in the appearance of the pink colour
as well as the spectral shift from 407 to 498 nm. This
did not only suggest a direct 2∶1 (F∶Zn) anion-cation
interaction, but showed that the colorimetric activities of
receptor 1 are not in any way inhibited by the presence
of ZnII. The ON and OFF reversible process sorely de-
pends on the concentrations of the anions. The stability
of receptor 1 was further demonstrated when about 4
cycles (ESI, Figure S8) were tested on F－/ZnII input-
output system, which displayed consistent results with
regard to anionic-cationic molar interactions. Moreover,
apart from the 4 cycle completed only, the system could
still carry on with more cycles, as there was still no sign
of interference with colour or spectral change patterns,
except the increase in input volumes. The IMP (implica-
tion) gate which is output-complementary to an INH
(inhibition) was affirmed. In Table 2 the corresponding
chemical inputs, spectral output signals and their binary
encoding are compiled and displayed. IMP logic is
closely related to “if…(condition), then…(conse-
quence)” phrases. These logic gates can be combined in
a complementary output circuit whose electronic
equivalents are indicated in Figure 4b.[15a,15f]
IMP
Input1
Input2
Output1
Output2
INH
b
Figure 4 (a) UV-Vis spectra of receptor 1 (1×10－5 mol•L ) in
DMSO with F－ and molecular logic function “IMP” (407 nm)
and “INH” (498 nm), (I) receptor 1＋4 equiv. F－, (II) receptor 1
＋ZnII, (III) receptor 1＋4 equiv. F－＋2 equiv. ZnII, (IV) receptor
1. (b) A combinatorial IMP/INH logic circuit.
－
1
Table 2 Truth table for the logic behavior IMP/INH of receptor
1 (10 μmol•L－1 in DMSO)a
Output
(IMP)
407 nm (Abs.) 498 nm (Abs.)
Input
Input 1 (F－) Input 2 (ZnII)
(INH)
0
1
0
1
0
0
1
1
1 (0.26)
0 (0.08)
1 (0.28)
1 (0.25)
0 (0.04)
1 (0.29)
0 (0.02)
0 (0.07)
Figure 5 1H NMR spectra taken during the titration of receptor
1 in DMSO-d6 solution (1.0×10－ mol•L－1) with a standard
5
a Inputs: 4 equiv. F－ and 2 equiv. ZnII. Outputs: absorbance in-
tensity at 407 and 498 nm, respectively.
solution of TBAF ranging from 1∶0—2 molar equivalents and
the addition of ZnII to receptor 1…F reversing the system.
1H NMR titrations in DMSO-d6
peared upon the gradual addition of F－ , before a
bifluoride ion (HF2)－ signal appeared at δ 15—17. Ob-
viously, at low F－ (0.5—1 equiv.) a 1∶1 binding ratio
was formed with receptor 1, suggesting hydrogen-bond
formation as shown in equation (1), however, as F－
increased (1.5—2 equiv.) the HF is released from the
H-bond complex giving rise to (HF2)－ complex[17,18]
and the deprotonated receptor, shifting the interaction
ratio to a 2∶1 (F∶receptor 1) as indicated in equation
(2).[20]
In order to investigate and ascertain the binding ac-
1
tivities of the receptor, H NMR titrations were carried
out in the DMSO-d6 molar solution of receptor 1. It is
1
noticed that the H NMR spectra suggested that the in-
teraction of F－ with receptor 1 is a two-step process: (i)
formation of F…HN hydrogen-bond complex at low F－
and (ii) the deprotonation when F－ is in excess. Accord-
ing to Figure 5, receptor 1 exhibits one resonance at δ
11.70 attributed to the binding proton (—NH).[4c,5,6c,10c]
The NH proton signal broadened downfield and disap-
At low F－ concentration (hydrogen bonding):
Chin. J. Chem. 2012, XX, 1—7
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5

Uahengo et al.
FULL PAPER
LH (receptor 1) F－↔[LH F]－
(1)
(2)
P. A.; Cho, W. S. Anion Receptor Chemistry, Royal Society of
Chemistry, Cambridge, 2006.
＋
…
Excess F－ concentration (deprotonation):
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LH 2F－↔L [FHF]－
＋
＋
Moreover, the phenyl ring protons Ha, Hb, and Hc
(Scheme 1) all experienced significant upfield shifts,
which could be attributed to the increase in electron
density on the phenyl ring owing to the through-bond
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1
effect.[13a] More details on H NMR titration spectra are
referred to ESI, Figure S9, 10.
Conclusions
In summary, the phenylyhydrazone based anion re-
ceptor 1 was successfully synthesized and analyzed in
DMSO. There are two vital points which can be de-
duced from this sensor: (i) receptor 1 is selective for
AcO－ and F－, displaying visual changes detectable by
naked eyes or without any instrument; (ii) receptor 1
displayed a remarkable reversible system based on two
input complementary IMP/INH logic functions modu-
lated by F－/ZnII, which is very rare in literature. The
colorimetric switching by appropriate amounts of anion
and cation is likened to a molecular logic gate based on
two-input functions for ON and OFF system control.
Acknowledgement
This work was supported by the National Natural
Science Foundation of China (No. 21101121), the
Natural Science Fund (No. 2010CDB01301) of Hubei
Province and Dalian University of Technology State
Key Laboratory of Fine Chemicals Fund (No. KF0912).
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