Author's Accepted Manuscript

A chromone Schiff-base as Al(III) selective

fluorescent and colorimetric chemosensor
Long Fan, Jing-can Qin, Tian-rong Li, Bao-dui
Wang, Zheng-yin Yang

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PII: S0022-2313(14)00357-3
DOI: http://dx.doi.org/10.1016/j.jlumin.2014.06.023
Reference: LUMIN12750

To appear in: Journal of Luminescence

Received date: 10 January 2014

Revised date: 8 February 2014
Accepted date: 12 June 2014

Cite this article as: Long Fan, Jing-can Qin, Tian-rong Li, Bao-dui Wang, Zheng-
yin Yang, A chromone Schiff-base as Al(III) selective fluorescent and
colorimetric chemosensor, Journal of Luminescence, http://dx.doi.org/10.1016/j.
jlumin.2014.06.023

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A chromone Schiff-base as Al(III) selective fluorescent and

colorimetric chemosensor
Long Fan, Jing-can Qin, Tian-rong Li, Bao-dui Wang, Zheng-yin Yang*

College of Chemistry and Chemical Engineering, State Key Laboratory of Applied Organic

Chemistry, Lanzhou University, Lanzhou 730000, P.R. China

**Corresponding author. Tel.: +86 931 8913515; Fax: +86 931 8912582; e-mail:

yangzy@lzu.edu.cn (Z.Y. Yang)

Abstract: A novel and simple chromone Schiff-base receptor

7-methoxychromone-3-carbaldehyde-(indole-2-formyl) hydrazone (MCIH) was prepared.

Among the various metal ions, only Al3+ induces the fluorescence enhancement and results in

“OFF-ON” type sensing with excellent selectivity and high sensitivity in ethanol system. Upon

binding of Al3+, a significant fluorescence enhancement with an “OFF-ON” ratio over 500-fold

was triggered and it features visible light excitation (423 nm) and emission (507 nm) profiles.

However, other metal ions had no such significant effect on the fluorescence. Also, MCIH can

severe as a highly selective chemodosimeter for Al3+ with “naked-eye” detection, which is easily

observed from colorless to yellow-green. The detection limit of MCIH for Al3+ detection was as

low as 5×10-8 M level.

Keywords: fluorescence sensor; colorimetric; aluminum ions; detection limit; chromone;

Schiff-base;

 1
 

1. Introduction

Aluminum, as the third most abundant metallic element on Earth, was found to be

neurotoxic to organisms a long time ago [1]. Al3+ ion existing in natural waters and most plants

can enter the human body through foods and water [2]. Excessive exposure of the human body to

Al3+ leads to a wide range of diseases. For example, Al3+ has an important role in Alzheimer’s

disease, Parkinson’s disease, chronic renal failure, bone softening and smoking related diseases.

Since there is a close association between Al3+ and human health, the investigation of reliable

detection methods for Al3+ becomes more and more important [3-8]. In recent decades, many

fluorescent chemosensors of different metal ions have been paid a great attention specific for

Zn2+, Hg2+, Cu2+ or other transition metals. Compared to the metal ions, only a few fluorescent

chemosensors have been reported for detection of Al3+ [9-15]. The detection of Al3+ has always

been problematic due to the lack of poor coordination ability and spectroscopic characteristics

[16-17]. For practical applications, it is necessary to develop Al3+ sensors that are easily prepared

and possess selective and sensitive signaling mechanisms [18]. Recently, considerable attention

has been focused on colorimetric and fluorometric online detection ways for Al3+, known for

their selectivity and simplicity.

In general, as Al3+ is a hard-acid, it has been found that Al3+ prefers a coordination sphere

containing N and O as hard-base donor sites. A large number of Schiff’s bases can be used as

Al3+ sensors. On the other hand, As a chemosensor, a Schiff base is popular owing to its good

photophysical properties [19-20]. Schiff-bases and their complexes have various applications in

clinical, biological and analytical fields. Keeping this in mind,

7-methoxychromone-3-carbaldehyde and 1H-indole-2-carboxylic acid hydrazide were selected

 2
 

as the reactants to obtain the Schiff base. It is used as an efficient fluorescent probe for the

determination of Al3+ in ethanol.

Herein, we report a chromone Schiff-base as a fluorescent “OFF-ON” sensor for distinct

detection of Al3+ ions in ethanol. The probe exhibits remarkably enhanced intensity in its

fluorescence emission in presence of Al3+ in ethanol over other metal ions examined. This

restricts the photoinduced electron transfer (PET) process and enhances the fluorescence output

of MCIH via chelation-enhanced fluorescence (CHEF) effect. The method of Job’s plot

confirmed the formation of 1:2 between Al3+ and MCIH. The free chemosensor MCIH shows

no fluorescence emission. Upon binding of Al3+ ions, a significant fluorescence enhancement

with “OFF-ON” ratios over 500-fold was achieved in ethanol.

2. Experimental

2.1. Materials and instruments

All reagents for synthesis obtained commercially were used without further purification. All

the used metal ions are form nitric acid salt. 1H NMR spectra were measured on a Bruker 400

MHz instruments using TMS as an internal standard. UV-Vis absorption spectra were

determined on a Shimadzu UV-240 spectrophotometer. ESI-MS analyses were performed using

a Bruker esquire 6000 spectrometer. Fluorescence spectra were recorded on a Hitachi RF-4500

spectrophotometer equipped with quartz cuvettes of 1 cm path length. IR spectra were obtained

in KBr discs on a Therrno Mattson FTIR spectrometer in the 4000–400cm-1 region. The melting

points of the com- pounds were determined on a Beijing XT4-100x microscopic melting point

apparatus.

 3
 

2.2. Synthesis

7-methoxychromone-3-carbaldehyde was obtained according to the literature procedures

[21]. Synthesis of MCIH was based on the following method (Scheme 1): an ethanol solution

(12 mL) of 1H-indole-2-carboxylic acid hydrazide (0.175 g, 1 mmol) was added dropwise to a

solution (20 mL) of 7-methoxychromone-3-carbaldehyde (0.204 g, 1 mmol) in ethanol. Then the

solution was reflux for 4h under stirring and some pale yellow precipitant appeared. The mixture

was filtered and dried under vacuum. Recrystallization from ethanol gave

7-methoxychromone-3-carbaldehyde-(indole-2-formyl) hydrazone (MCIH), which was dried

under vacuum. Yield, 68.2%, m.p: 231–234oC. 1H NMR (DMSO-d6, 400 MHz):  11.99 (s, 1H,

-NH-), 11.83 (s, 1H, H11), 8.81 (s, 1H, H4), 8.63 (s, 1H, H5), 8.07 (d, J = 8.0 Hz, 1H, H3), 7.70 (d,

J = 8.0 Hz, 1H, H7), 7.48 (d, J = 8.0 Hz, 1H, H10), 7.35 (s, 1H, H6), 7.26 (s, 2H, H8 and H9 ), 7.16

(s, 1H, H2), 7.10 (d, 1H, J = 8.0 Hz, H1)3.94 (s, 3H, -CH3) (Figure S1). MS (ESI) m/z 362.3

(M+H)+. IR (KBr) cm-1: 3235, 1656, 1628, 1562.

2.3. Analysis

Stock solutions (5 mM) of the nitrate salts of Li+, Na+, K+, Cr3+, Cu2+, Hg2+, Pb2+, Ba2+, Fe3+,

Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+, Zn2+ and Al3+ in ethanol were prepared. Stock

solutions of MCIH (5 mM) were prepared in ethanol solution. Test solutions were prepared by

placing 20 L of the probe stock solution into cuvettes, adding an appropriate aliquot of each

ions stock, and diluting the solution to 2 mL with ethanol solutions. Both the excitation and

emission slit widths were 3.0 nm.

 4
 

3. Results and discussion

3.1. Absorption studies

Aluminum ions induced a significant change in the absorption spectrum of the reagent. The

colorless solution of MCIH exhibited a broad band around 323 nm. Upon addition of Al3+ ions,

the absorbance bands at 416 nm, 437 nm and 463 nm enhanced. The clearly isosbestic point at

360 nm indicated the formation of a stable MCIH-Al3+ complex (Figure 1). The significant

change to wavelength resulted in a color change from colorless to yellow-green, which can be

easily observed by the “naked-eye”. Addition of other representative metal ions (5.0 equ.) such

as Li+, Na+, K+, Cr3+, Cu2+, Hg2+, Pb2+, Ba2+, Fe3+, Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+,

Zn2+ did not give rise to significant color changes. These results suggest that MCIH could be

served as a potential “naked-eye” sensor selective for Al3+ (Figure 2) [22-25].

3.2. Emission studies

MCIH forms colorless and nonfluorescent solutions in organic solvents, including ethanol,

methanol, acetonitrile, (dimethyl formamide) DMF, (tetrahydrofuran) THF and

(dimethylsulfoxide) DMSO. Addition of aluminum ions to MCIH in ethanol and methanol leads

to the development of a yellow-green color and yellow-green fluorescence (Figure S2).

A fluorescence study was further used to determine the selectivity and sensitivity of MCIH

in the presence of various metal ions, such as Li+, Na+, K+, Cr3+, Cu2+, Hg2+, Pb2+, Ba2+, Fe3+,

Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+ and Zn2+. MCIH itself was non-fluorescent in

ethanol. Fascinatingly, treatment of MCIH (50.0 M) with Al3+ (50.0 M) resulted in a strong

increase in the fluorescence intensity in the emission spectrum at 507 nm upon excitation at 423

nm (Figure 3). Interestingly, no such effect was observed when MCIH was treated with a large

 5
 

number of other cations (5.0 equ.). The probe exhibited high selectivity for Al3+ over other metal

ions.

PET mechanism involves the deactivation of the excited state of a fluorophore by addition

of an electron to one of its excited-state frontier orbitals. This leaves the fluorophore in a

nonemissive state. For example, the free electron pair of a functional group attached to the

fluorophore may quench its fluorescence intramolecularly due to a PET process. Metal

coordination to this group renders it a less efficient electron donor, thereby interrupting the PET

process and enhances the fluorescence output via chelation-enhanced fluorescence (CHEF)

effect [26-28]. Here, the emission intensity of MCIH is very low, it is due to quenching by the

Schiff-base nitrogen long pair electrons through a PET mechanism. With increasing of Al3+

(0-1.0 equ.), the emission intensity of MCIH (50.0 M) at 507 nm increased more than 500-fold

(Figure 4). The chelation of Al3+ with the carbonyl of chromone moiety, the nitrogen atom of the

–C=N group and the carbonyl of 1H-indole-2-carboxylic acid hydrazide moiety lead to the PET

process was suppressed, the fluorescence of the system was restored. [29-30].

To explore the possibility of using MCIH as a practical selective fluorescent chemosensor

for Al3+, competition experiments were carried out. For this purpose, MCIH was treated with 1.0

equ. of Al3+ in the presence of 5.0 equ. of other metal ions. Relatively low interference was

observed for the detection of Al3+ in the presence of other metal ions (Figure 5). MCIH

responding for Al3+ in the presence of Fe2+ and Fe3+ are relatively low but clearly detectable.

Therefore, MCIH was shown to be a promising selective fluorescent probe for Al3+ in the

presence of most competing metal ions.

 6
 

3.3. Binding studies

In order to determine the stoichiometry between MCIH and Al3+, the method of continuous

variation (Job's plot) was used. The total concentration of the MCIH and Al3+ was constant (20.0

M), with a continuous variable molar fraction of guest ([MCIH] / [MCIH] + [Al3+]). Figure S3

shows the Job's plot of MCIH with Al3+ (at 507 nm), the MCIH-Al3+ complex concentration

approaches a maximum when the molar fraction of Al3+ is 0.67, indicating a 2:1 stoichiometry

complex was formed, In addition, the formation of a 2:1 complex between MCIH and Al3+ was

further confirmed by the appearance of a peak at m/z 747.3, assignable to [2MCIH – 2H + Al3+]+

in the ESI-MS (Figure S4).

In IR spectra, the stretching frequency of the carbonyl of chromone moiety decreased by

~16 cm-1, the -C=N and the amide carbonyl were decreased by ~44 cm-1 and ~5 cm-1 upon Al3+

binding and suggests coordination to the two carbonyl oxygen atoms and the nitrogen atom of

–C=N group. The band at 603 cm-1 or so was assigned to (Al-O), which demonstrated formation

of a coordinative bond between aluminum and oxygen. Correspondingly, the (Al-N) was at 403

cm-1 or so (Figure S5) [31].

NMR studies provide additional evidence of the interaction between MCIH and Al3+. 1H

NMR spectra of MCIH were recorded in DMSO-d6 upon the addition of Al3+. Significant

spectral changes were observed as shown in Figure 6. The signals of –NH–, H3 were up-field

shifted 0.03, 0.08 and H5, H11 were down-field shifted 0.05, 0.01 respectively, while the signals

of the other protons remained nearly unchanged (Table 1). This indicated that the direct

involvement of the carbonyl of chromone moiety, the nitrogen atom of the –C=N group, the

carbonyl of indole-2-formyl hydrazone moiety coordinate with Al3+.

 7
 

As shown in Figure S6, the association constant Ka of the complex was calculated to be

7.8×103 M-1 with a linear relationship by the Benesi-Hildebrand equation (Eq. (1)) [32], where

Fmax, F, and Fmin are fluorescence intensities of MCIH in the presence of Al3+ at saturation, any

intermediate Al3+concentration, and free MCIH. [33-34].

(1)

To reflect the high sensitivity, the detection limit of MCIH in recognizing Al3+ was

evaluated by using fluorescence spectra (Fig. S7). Upon addition of 0.05 to 0.25 M Al3+ to the

sensor MCIH, fluorescence emission enhancement demonstrated that this sensor could detect

Al3+ at 5×10-8 M level, which is low for the detection of Al3+ ions found in many chemical

systems [35-36]. Fluorescence quantum yield measurements were carried out for the sensor to

understand its fluorescence behavior observed. The fluorescence quantum yield of MCIH in the

free andAl3+-bound state was found to be 0.05 and 0.32, respectively.

Reversibility is a prerequisite in developing novel chemosensors for practical application.

The reversibility of the recognition process of MCIH was performed by adding an Al3+ bonding

agent, Na2EDTA. The addition of Na2EDTA to a mixture of MCIH and Al3+ resulted in

diminution of the fluorescence intensity at 507 nm, and the fluorescent intensity was recovered

by the addition of Al3+ again, which indicated the regeneration of the free chemosensor MCIH

(Figure S8). Such reversibility and regeneration are important for the fabrication of devices to

sense the Al3+ ions.

 8
 

4. Conclusion

In summary, we have developed a novel sensor MCIH based on PET and CHEF

mechanism. The chemosensor showed high selectivity for Al3+ over other metal ions with

500-fold fluorescence enhancement and high sensitivity with the detection limit reaching at

5×10-8 M level in ethanol. The probe exhibited an excellent “OFF-ON” fluorescence signal with

high sensitivity in the presence of Al3+, allowing its reversible detection in the presence of a wide

range of environmentally relevant competing metal ions. More importantly, the detection limit

was sufficiently low to detect the submicromolar concentration of the Al3+. Thus, we believe

MCIH has the ability to serve as a practical probe for Al3+ detection in environment and

biological systems. This strategy may provide a general method for designing new PET

chemosensor to detect other biologically and environmentally relevant species.

Acknowledgments

This work is supported by the National Natural Science Foundation of China (81171337),

Gansu NSF (1308RJZA115).

 9
 

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Figure captions

Figure 1. The absorbance of MCIH in ethanol (50.0 M) after addition of Al3+ (0, 0.2, 0.4, 0.6,

0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0 equ.).

Figure 2. (top) Absorption changes of MCIH (50.0 M) upon addition of different metal ions

(5.0 equ.); (bottom) The photograph of MCIH after addition of different metal ions.

Figure 3. (top) Fluorescence responses of MCIH (50.0 M) in ethanol with 5.0 equ. of Li+, Na+,

K+, Cr3+, Cu2+, Hg2+, Pb2+, Ba2+, Fe3+, Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+, Zn2+ and

1.0 equ. of Al3+. Excitation wavelength was 423 nm; (bottom) The photograph of MCIH after

addition of different metal ions under UV lamp.

 12
 

Figure 4. Fluorescence emission spectra of MCIH (50.0 M) in ethanol upon the addition of

Al(NO3)3 (0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 equ.) with an excitation of 423 nm. Inset:

color of MCIH and MCIH+Al3+ system under UV lamp.

Figure 5. Relative fluorescence of MCIH and its complexation with Al3+ in the presence of

various metal ions. Blue bar: MCIH (50.0 M) and MCIH with 5.0 equ. of Li+, Na+, K+, Cr3+,

Cu2+, Hg2+, Pb2+, Ba2+, Fe3+, Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+, Zn2+ stated. Red bar:

50.0 M of MCIH with respective competing metal ions (5.0 equ.) and Al3+ (1.0 equ.) stated.

Figure 6. Proposed binding mode for interaction of Al3+ with MCIH and 1H NMR spectra of

MCIH with Al3+ in DMSO-d6: (I) MCIH (top); (II) MCIH with Al3+ (bottom).

Scheme1. Synthesis of 7-methoxychromone-3-carbaldehyde-(indole-2-formyl) hydrazone

(MCIH).

Table 1. Changes in chemical shift of related protons in NMR titration.

 NH  H3  H5  H11 

(ppm) Changein (ppm) Changein (ppm) Changein (ppm) Changein
MCIH 11.99  8.07  8.63  11.83 
3+
MCIH+Al  12.02 0.03 8.15 0.08 8.58 0.05 11.82 0.01
(upfield) (upfield) (downfield) (downfield)





• An easy-to-make colorimetric and fluorescent sensor for Al3+ was developed.
• The sensor exhibits higher selectivity and sensitivity for Al3+ than other metal ions.
• Al3+ resulted in an instant color change of MCIH from colorless to yellow-green.
• The Al3+ detection limit reaching at 5×10-8 M level in ethanol.
• This sensor features visible light excitation (423 nm) and emission (507 nm) profiles.

 13
Figure 1. The absorbance of MCIH in ethanol (50.0 μM) after addition of Al3+ (0, 0.2, 0.4, 0.6,

0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0 equ.).

14
Figure 2. (top) Absorption changes of MCIH (50.0 μM) upon addition of different metal ions

(5.0 equ.); (bottom) The photograph of MCIH after addition of different metal ions.

15
Figure 3. (top) Fluorescence responses of MCIH (50.0 μM) in ethanol with 5.0 equ. of Li+, Na+,

K+, Cr3+, Cu2+, Hg2+, Pb2+, Ba2+, Fe3+, Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+, Zn2+, and

1.0 equ. of Al3+. Excitation wavelength was 423 nm; (bottom) The photograph of MCIH after

addition of different metal ions under UV lamp.

16
Figure 4. Fluorescence emission spectra of MCIH (50.0 μM) in ethanol upon the addition of

Al(NO3)3 (0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 equ.) with an excitation of 423 nm. Inset:

color of MCIH and MCIH+Al3+ system under UV lamp.

17
Figure 5. Relative fluorescence of MCIH and its complexation with Al3+ in the presence of

various metal ions. Blue bar: MCIH (50.0 μM) and MCIH with 5.0 equ. of Li+, Na+, K+, Cr3+,

Cu2+, Hg2+, Pb2+, Ba2+, Fe3+, Fe2+, Mn2+, Co2+, Ca2+, Ag+, Cd2+, Ni2+, Mg2+, Zn2+ stated. Red bar:

50.0 μM of MCIH with respective competing metal ions (5.0 equ.) and Al3+ (1.0 equ.) stated.

18
Figure 6. Proposed binding mode for interaction of Al3+ with MCIH and 1H NMR spectra of

MCIH with Al3+ in DMSO-d6: (I) MCIH (top); (II) MCIH with Al3+ (bottom).

19
Scheme1. Synthesis of 7-methoxychromone-3-carbaldehyde-(indole-2-formyl) hydrazone

(MCIH).

20