Chalcone scaffolds as photofunctional hybrid material of indolin-2-one-functionalized siloxy framework for optical sensing of Cu2+

Article abstract of DOI:10.1039/c8nj02884b

Owing to their easy approachability and high degree of structural and functional diversity, many multicomponent reactions such as 1,3-dipolar cycloaddition have been a rich source of conjugated π-systems, functionalised chromophores and active molecules. Despite their high potential for investigation and practical benefits, few products have thus far been scrutinized for their metal sensing abilities. In the present study, indolin-2-one chalcones bearing siloxy molecular systems were synthesized by a [2+3] cycloaddition-based reaction sequence. A designed chemosensor exhibited an optical (absorption spectra) response toward Cu²⁺ ions in an acetonitrile solution. Different aspects of the sensing phenomena such as selectivity and association constants were studied in detail using UV-vis spectroscopy. The calibration plot was linear (R² = 0.9966) over a large range of Cu²⁺ ion concentrations (10 μM). This novel effort has initiated a well-organized method for the efficient improvement of cation sensors with triazole for detecting heavy metal pollutants in environmental and healthcare fields on a large scale.

Full text of DOI:10.1039/c8nj02884b

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A. Arora, A. Singh, G. Sharma, S. Gawri and P. Satija, New J. Chem., 2018, DOI: 10.1039/C8NJ02884B.
Volume 40 Number
1
January 2016 Pages 1–846
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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

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Chalcone scaffolds as photo functional hybrid material of indolin-2-one functionalized
2
+
siloxy framework for optical sensing of Cu
a, *
a
b
a
a
Gurjaspreet Singh , Pooja Kalra , Aanchal Arora , Akshpreet Singh , Geetika Sharma ,
a
a
Sanchita , Pinky Satija
a
Department of Chemistry and Centre of Advanced Studies, Panjab University, Chandigarh,
160014, India
b
Khalsa College for Women, Civil Lines, Ludhiana, Punjab, 143002, India
*
Corresponding Author
Dr. Gurjaspreet Singh
Associate Professor
Department of Chemistry and Centre of Advanced Studies
Panjab University, Chandigarh, India
+
91ꢀ0172ꢀ2534428
Email: gjpsingh@pu.ac.in
Abstract
Owing to their easy approachability and high degree of structural and functional diversity,
many multicomponent reactions like 1,3ꢀdipolar cycloaddition have been a rich source of
conjugate πꢀsystems, functionalised chromophores active molecules. Despite their high
explorative potential and practical benefits, only a few products have been so far scrutinized
for their metal sensing abilities. In the present report, indolinꢀ2ꢀone chalcones bearing siloxy
molecular systems have been synthesized by [2+3] cycloaddition based sequence. Designed
2
+
chemosensor exhibited optical (absorption spectra) response toward Cu ion in acetonitrile

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solution. Different aspects of the sensing phenomena such as selectivity, association
constants, etc were studied in detail using UVꢀVis spectroscopy. The calibration plot is linear
2
2+
(
r : 0.9966) over the large Cu ions concentration ranges (10 µM). This novel effort is
initiated a wellꢀorganize way of efficient cationic sensor improvement with triazole for heavy
metallic pollutants in environmental and healthꢀcare fields in large scales.
Keywords: Indolinꢀ2ꢀone • 1,2,3ꢀtriazole • Microwave synthesis • Chemo sensor • Cation
sensing
Introduction
Disclosure of novel molecular systems with unique photo physical attributes is scientifically
exciting and intellectually exigent task. Use and development of new chemo sensors for the
efficient detection of trace metal ions remain as an important research topic in environmental
1
investigations . Sensing metal ions continues to be an established field of research with
2
ꢀ3
hundreds of reports every year . Generally, industrial waste water always contains a variety
of heavy metal ions at the same time. Thus, development of new receptors for the detection of
4
single metal selectively in presence of other is an emerging area of great interest . As the
third most abundant trace element in human body, the average concentration of copper in
5
human organism is about 15.7–23.6 ꢁM . It participates in some vital biochemical reactions
and thus plays an important role in many biological processes. Both lacking and excess intake
of copper can initiate negative effects or even harmful symptoms on human health, including
some serious diseases such as amyotrophic lateral sclerosis, Wilson disease, Alzheimer
6
–8
disease and Prion disease . As a consequence, U.S. Environmental Protection Agency has
fixed a ceiling limit of copper for drinking water as 20ꢁM. The signifying and quantification
of copper thus becomes an important issue in chemical analysis and environmental
protection.

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Considering the public health concerns, finding practical ways for simultaneous detection of
cations, and developing optical chemosensors has arisen as an area of escalating importance.
Several detection methods, including atomic absorption, electrochemical, voltammetric,
potentiometric and optical methods as well as ionꢀexchange chromatography have been
9
ꢀ13
explored . Among the different methods sensors as optical methods are preferred and
widely used because of their advantages, such as costꢀeffectiveness, rapidity, realꢀtime
14ꢀ17
monitoring, and lack of equipment required
. Considering the vital role of newly designed
hybrid in ion sensing, the development of probes for scientists is still a challenging area.
Metal organic frameworks which are constructed from the readily selfꢀassembled metal
1
8ꢀ
cations and appropriate organic ligands, have obtained widely attentions in various fields
2
0
.
The wellꢀdefined topologies and structural rigidity make them have several potential
21ꢀ23
applications as functional materials in wide fields, such as gas storage/separation,
24ꢀ25
26ꢀ27
28ꢀ29
catalysis,
drug delivery
and chemical sensors
. The ligands can be rationally
designed and modified with multifunctional groups, such as triazoles, and other conjugated
system that provide binding sites are tailored to specifically interact with analytes to detect
and recognise various cations, anions, small molecules on their optical response.
For a typical sensing procedure, a sensor usually recognizes the metal ion by forming a large
3
0ꢀ32
conjugation plane with the analyte, showing a red shift of electronic transition
. In
addition, the combination of various analytes and their adding sequence can lead to various
responses of optical sensors, which further widens their applications. The purpose of this
2
+
paper is (1) to recognise the chromophoric portion of the molecules responsible for Cu
recognition (2) to determine the role of basic molecular framework and substituent pattern in
sensing applications (3) to examine the utility of titled compounds in metal sensing. If
successful, this work can be expanded in multiple directions; notably, a large number of isatin
chalcone based siloxy frameworks with suitable substituent patterns can be synthesized and

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studied for their structural property relationship to get deeper insight into underlying sensing
mechanism. Keeping all these things in mind, we decided to explore the sensing properties of
isatin chalcone based siloxy compounds. Among many factors that look decisive for the
development of this field is the synthetic accessibility of these systems. Generally, it is highly
desirable that these scaffolds originated from a simple, clean and easy synthetic route which
33ꢀ34
also aligns well with the current idea of “green chemistry”
. Considering green chemistry
so microwave assisted method has been opted for synthesis. Herein, we aim to synthesize the
isatin triazole probes derived from isatin based chalcone acetylenic unit and 3ꢀ
azidopropyltriethoxysilane, which has highly conjugated and oxygen rich coordination
2+
environment and could provide coordination sites for Cu .
Results and discussions
Synthesis and characterizations
Fig 1. Reaction Pathway
For both the step 1 and step 2 predominantly two routes were determined microwave and
conventional. (Fig.1.) for step 1 first path was the conventional which requires time of
7
1
20mins at refluxing and second route opted was microwave with reduction in time to
5mins at 140 ºC. In addition to this for step 2 analogous approach was opted to draw a strict
comparisons between time, effectiveness and energy costs. For the step 2 basic conventional

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path needs 240 mins at refluxing for completion. On the other hand microwave irradiation
path has lessened the time to 5 mins at 100 º C. Traditionally, organic synthesis is carried out
by conductive heating with an external heat source. This is a comparatively slow and
inefficient method for transferring energy into the system, since it depends on the thermal
conductivity of the various materials that must be penetrated, and results in the temperature
of the reaction vessel being higher than that of the reaction mixture. Microwaveꢀenhanced
chemistry is based on the efficient heating of materials by “microwave dielectric heating”
effects. This phenomenon is dependent on the ability of a specific material (solvent or
reagent) to absorb microwave energy and convert it into heat. Under MW irradiation
conditions, organic reactions can be accelerated and selectivities of the ensuing products can
be obtained by choosing appropriate MW parameters, thus offering several advantages over
conventional heating, such as instantaneous and rapid heating (deep inside heating), high
3
5ꢀ37
temperature homogeneity, and selective heating.
Here we have synthesized a novel
substituted 1, 2, 3ꢀtriazole indolinꢀ2ꢀone siloxy frameworks derivatives from Indolinꢀ2ꢀone
chalcone appended acetylene (ICAA) and 3ꢀazidopropyltriethoxysilane under microwave and
classical conditions. In general, improvements in rates and yield of reactions are observed by
carrying out the reactions under the influence of microwave irradiations. Here goal is to
develop cleaner technologies for green chemistry. Among the several aspects of green
chemistry, using efficient and less hazardous energy sources such as microwave energy is
much needed.
General detail of UV absorption experiment
All of the recognition studies were accomplished at 25 °C, and bounteous time was provided
for the solutions to become consistent before the spectra were recorded. The sensing abilities
+
+
+
2+
2+
of all of the compounds were scrutinized through the addition of Na , Li , K , Mg , Ca ,
3
+
2+
2+
3+
2+
3+
2+
2+
2+
2+
2+
+
2+
Al , Cu , Ni ,Cr , Fe , Fe , Co , Zn , Ba , Cd , Hg Ag and Pb cations (up to 2

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equiv.) to CH
3
CN solutions of each receptor. As observed in Fig. 2a, the UV–vis spectrum of
CN exhibits two main bands centered at 260 and 340 nm. Upon
analyte ICAA silane in CH
3
2
+
addition of Cu ion, a strong band appears at 460 nm and 315nm. The other metal ions tested
did not exhibit formation of any new band even in excess amount. The binding ability
depends on size, charge and electron configuration of the metal ion and ligand, which are
2+
very suitable for the Cu with probe InꢀCh (indolinꢀ2ꢀone chalcone) to form a complex. In
the metal complexes indolinꢀ2ꢀone containing ligands, coordination can occur through O
atom or –C=CH of chalcone moiety separately or both simultaneously. The incorporation of
the triazole fragment into the ICAA group through azideꢀalkyne click silylation increases the
complexity of the binding system. Thus, increases the coordination sites of the molecular
system. To gain an insight into the sensing properties of InꢀCh as a receptor, a titration
2
+
experiment was carried out with the gradual addition (0 to 10 µM) of Cu ions to the InꢀCh
solution. As shown in Fig. 3, gradual increase in the absorbance band centered at 315nm and
2
+
4
60nm was observed with the increase in concentration of Cu ion. The sensor showed a
nice linear relationship between the absorbance at 315nm and the concentration of metal ions
2
+
Cu from 0.0 to 10 µM (Fig. 3), suggests that sensor InꢀCh is potentially applicable for
2
+
quantitative analysis of Cu with a large dynamic range. No further significant changes in
the absorbance of the system were observed at above10 µM (2 equiv.) of metal ions.
The UV/Vis titration experiments disclosed that the receptor (5a) possess exclusive response
2
+
toward copper ions (Fig 2). Specifically, the injection of Cu ions into the receptor solution
resulted in the enhancement of the absorption intensity and a simultaneous bathochromic shift
in the wavelength maxima. This trend may arise because increased conjugation on
complexation with copper ions leads to a decrease in the n–π* transitionꢀenergy difference.
As all of the compounds differs only in chromophoric unit like –F, ꢀCl, ꢀBr, ꢀOCH , etc so
3
identical perturbations in the presence of copper ions was observed.

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InꢀCh derivative possess major absorption bands in the region λ = 300ꢀ460nm, which confirm
the n–π* electronic transitions in the conjugated system. The absorption band in the region λ
2
+
=
300ꢀ460 nm, which confirm the n–π* electronic transitions from carbonyl O atom to Cu
ion. This is mainly due to the strong intramolecular charge transfer (ICT) interaction between
2
+
the O donor and Cu ion acceptors. The spectral characteristics of any chromophore depend
on its electronic environment and the degree of conjugation encircling it, which can together
allow a systematic fineꢀtuning. In the context of UV/Vis absorption as the Inꢀ Ch traizole unit
is prevalent in all derivatives, one can safely surmise that it is the change in chrmophoric unit
does not alter the sensing mechanism. The absorption spectra of synthesized InꢀCh systems
2
+
were characterized by two bands centred near 315 nm and 460 nm. Except Cu , excess
presence of other metal ions didn’t create any noticeable change either in band position or in
2
+
absorbance. The probe was found selective toward Cu and this sensing behaviour was
remained unaffected by the presence of other cationic species present in the analyte. The limit
of detection as calculated from the standard deviation of responses and slope of the curve
2
+
came out to be 3.21 µM that is below the limit assigned by WHO for Cu ion (20 µM).
2.5
2.0
1.5
1.0
0.5
0.0
2
+
2+
3+
2+
2+
2+
3+
2+
Analyte+Ni +Fe +Fe +Ba +Pb +Mg +Al +Cd
2+
+
2+
3+
2+
+
+
+
2+
+
Co +Ag +Ca +Cr +Hg +Li +k +Na +Zn
2+
Analyte+Cu
250
300
350
400
450
500
550
600
W va eel ng ht ( mn )

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Fig. 2. (a)UV–vis spectrum of analyte 5a (10µM) in the presence of various metal ions
10µM) in Acetonitrile. (b) A bar diagram showing the change in the absorbance of analyte at
λmax= 315nm.
(
2.5
2.0
1.5
1.0
0.5
0.0
2 equiv
2+
Cu
0
equiv
250
300
350
400
450
500
550
600
W va eel ng ht ( mn )
Fig.3. Family of UVꢀVis spectra taken in the course of the titration of 5a (10 µM inCH CN)
3
2+
with Cu ions (0–2 equiv. i.e. 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4,
.5, 1.6, 1.7, 1.8, 1.9, 2.0)
Binding Constant
1

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As the cationꢀrecognition properties of receptors 5a had been explored by examining UV/Vis
spectral changes upon the addition of different cations, the altered absorbance data could be
evaluated further through the modified Benesi–Hildebrand (B–H) equation to gauge the
38
comparative strength of different receptor towards the tested ion . In general, the B–H
relationship is used to determine the stoichiometry of complexation as well as the association
constant (Ka), a measure of the strength of the interaction between the receptor and the metal
ions in a complex. As the UV/Vis absorption plots (Figure 2) revealed the binding of the
chemoreceptor with copper ions, we first measured the stoichiometry of the complexation for
the compound. From the assessment of the titration data, a linear regression for the plot of (A
–
1
2+ –1
–
Ao) versus [Cu ] could be obtained for 5a.The binding constant for the formation of the
metal complex was estimated on account of the change in the absorbance at 315nm by
5
−1
considering a 1:1 binding stoichiometry and found to be 1.2×10 M for InꢀCh using Benesi
Hildebrand equation (Fig S24). Thus suggesting the strong interaction between the molecular
system and the cupric ions.
Mode of Binding
On the basis of geometrical preferences we visualised that ligands comprising a 1,2,3ꢀtriazole
bearing nitrogen donor atom, the π electron donor –C=Cꢀ group and additional coordination
sites in the substituent attached to the triazole unit could be suitable ligands for coordination
to metals in a suitable fashion. The retrosynthetic approach to the 1,2,3ꢀtriazoleꢀbased ligands
with nonꢀplanar coordination pockets containing π electron system depicted in Fig. 4. In
general, triazole structures use their nitrogens or π electron cloud of –C=Cꢀ to bind cations,
2
and their Csp ꢀH proton to bind the anions. The triazole group is a fascinating functional
group as it possesses the border π electron donor site as a binding sites. Consequently, the
presence of additional binding unit like oxygen attached to indolinꢀ2ꢀone facilities the
formation of corresponding metal complexes with metal ions. To date, research on exploring

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the binding attribute of triazole moiety has been scarce. The proposed binding mode is further
2+
supported by studying the binding behavior of compounds with Cu , being the borderline
acid display great affinity for borderline base coordination center oxygen on account of the
39
Hard and Soft Acid and Base (HSAB) concept.
2+
Fig. 4. : Proposed sensing mechanism of compound for Cu .
Spectroscopic Characterization
IR spectra
The neat vibrational spectroscopic data for all the newly synthesized compounds were
ꢀ1
recorded in the range of 4000ꢀ400 cm . The absorption frequencies were tuned to be in
agreement with the structure of the synthesized compounds. IR spectra of compounds showed
ꢀ1
a strong band at1720–1728 cm that attributed to indolinꢀ2ꢀone ν (C=O) stretching vibrations
ꢀ1
ꢀ1
of carbonyl bond. The blank region around 2100 cm and 3300 cm in silanes 5a-5e confirms
the cyclisation of acteylinic indolineꢀ2ꢀone chalcone moiety into triazole unit. Moreover,
ꢀ1
stretching vibrations of –C=CH of the triazole ring in the range of 2975ꢀ2964 cm adds on to
the confirmation of cycloaddition. Furthermore, SiꢀO stretching vibrations appear in all the
ꢀ1
ꢀ1
silanes in the range of 750ꢀ760 cm and 1060ꢀ1078 cm .

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NMR spectra
1
H NMR spectra of triethoxysilanes 5a-5e on keen observation revealed new fashion in
signals as depicted in NMR study of alkyne and azide framework before cycloaddition 4a-4e.
All the silanes 5a-5e displayed a set of multiplets due to –CH unit of propyl chain. The –
2
NCH linked to 1,2,3ꢀtriazole heterocycle was largely deꢀshielded which appeared at δ ~
2
5.40ꢀ5.29 ppm. In the NMR spectra of acetylinic indolinꢀ2ꢀone chalcone 4a-4e, alkynyl
proton appears around δ ~2.27ꢀ2.25 ppm that upon cyclisation with 3ꢀAzPTES shows a shift
to δ ~ 7.3ꢀ7.5 ppm 5a-5e validating the cyclisation of alkynyl moiety into triazole unit. The
aromatic ring protons were signaled as multiplets in the region δ~ 8.87–6.74 ppm. Moreover,
the –OCH protons appeared as singlet in the region δ~3.91 ppm. Any other effect due to
3
attachment of different substituents at aromatic ring of indolinꢀ2ꢀone chalcone was negligible
on propyl chain protons.
1
3
In C NMR spectra, For carbonyl carbon appears as the least shielded carbon in the region δ
~
168.3 ppm and spectra of all other compounds, the aromatic carbon appears as the least
shielded carbon in the region δ ~ 158.2ꢀ120.0 ppm. The methylene carbon of propyl chain
attached to silicon atom –C–Si– appeared as the most shielded carbon atom at around δ ~ 7.4
ppm for triethoxysilanes 5a-5eTwo carbons of alkynyl moiety 4a-4e appear in the range of δ
~
72.1ꢀ77.2ppm that shift around δ ~ 117.4ꢀ122.4 ppm and δ ~ 136.7ꢀ142.5 ppm in cyclised
compounds 5a-5e, that confirms the cyclisation of alkyne functionality to triazole unit.
Mass spectra
The mass spectra of all Inꢀch siloxy derivatives coincide with the projected structures and
have successfully depicted the respective molecularꢀion peaks with the addition of H+ or K+
ions. Mass spectral studies performed for some silanes 5c, 5d and 5e along with CHN
analytical study was performed on all alkynes (4a-4e) silanes (5a-5e) which proved the high
purity of all compounds. Molecular ion signals for compound 5c [MolecularMass: 585.66],

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+
+
+
m/z 586.3 [M+H ] for compound 5d [Molecular Mass:551.22], m/z 520.4 [M+K +4H ] and
+
+ +
m/z 596.4 [M+K +4H ] for compound 5e [Molecular Mass:536.69], confirmed the proposed
structure. Moreover, the elemental analysis performed on all alkynes and silanes justified the
purity of title compounds.
Experimental section
Chemical and reagents
Reagents such as Propargyl bromide (80% in toluene) (Aldrich China), substituted
benzaldehydes (AVERA, India), Isatin (AVERA, India), hydrazine hydrate(AVERA, India),
potassium carbonate (Thomas, India), sodium hydroxide (LOBA Chemie, India), sodium
sulphate (Finar, India), Bromotris(triphenylphosphine)copper(I) [CuBr(PPh ) ] (Aldrich,
3
3
USA) were used as received. Solvents were purified and dried before use. 3ꢀ
azidopropyltriethoxysilane (AzPTES) was synthesized by wellꢀknown method from literature
4
0
.
Instrument detail
Infrared spectrum was procured as Neat on a Thermo Scientific Fischer spectrometer. The
1
13
NMR spectra ( H and C) were recorded on BRUKER (400 MHz) spectrometer using CDCl
3
as internal reference and chemical shifts were reported relative to tetramethylsilane. J values
are given in Hz. The abbreviations are used: s, singlet; d, doublet; q, quartet; t, triplet; m,
multiplet. Melting points were measured in a Mel Temp II device using sealed capillaries and
were uncorrected. CHN analysis was obtained on Perkin Elmer Model 2400 CHNS elemental
analyzer and Thermo Scientific Flash 2000 organic elemental analyzer. . Mass spectral
measurements (TOF MS ESþ 1.38 eV) were carried out on Waters QQeTOF micro Mass
Spectrometer. Electronic spectral measurements were carried out using JASCO Vꢀ530 double
beam spectrophotometer. Microwave synthesis was carried out in Anton Paar Microwave
PRO reaction system.

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Microwave irradiation experiment
Microwave reactions were conducted using Anton Paarmonowave synthesizerꢀ600®.This
machine supplies a continuous flow of microwave energy with a selectable output power
option from 0 to 600W. All the reactions were carried in a high quality borosilicate process
vial, capped with a Teflon (PTFE) septum. At the beginning, Microwave radiations of
required power were used to attain a desired temperature. Once this temperature was reached,
the reaction vial was held to this temperature for suitable time. Finally, the reaction mixture
was cooled to room temperature by a fast adiabatic air jet.
General procedure for the synthesis for the synthesis of indolin-2-one from isatin
Isatin (1 equiv) was dissolved in 10 ml of EtOH followed by the addition of hydrazine
hydrate (1equiv/Isatin).The resulting mixture was allowed to reflux for 3 hours. After 3 hours
of refluxing NaOH pellets (3 equiv/isatin) was subsequently added and again the mixture was
refluxed for 0.5 hours. This mixture was allowed to cool to room temperature. After that
150ml of distilled water was added to the above mixture then mixture was acidified by
adding 2N HCl. The pH of the mixture was adjusted to 2 then the resulting solution was
extracted twice with the DCM. The organic filterate obtained was washed twice with the
brine solution and dried over the sodium sulphate. The above filtrate was concentrated to
obtained the indolinꢀ2ꢀone as a desired product.
General conventional approach for the synthesis of indolin-2-one linked chalcones
To a solution of the indolinꢀ2ꢀone (1.0 eq) in EtOH was added 2 drops of piperdine. The
resulting mixture was stirred at 25°C for 30 min. An ethanolic solution of the commercially
available substituted aldehyde (1.0 equiv) was subsequently added dropwise and the mixture
was refluxed for a period of 16 h at the 60 °C. The reaction was monitored by TLC and on
consumption of starting materials. After the reaction mixture was cooled the precipitates

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obtained was filtered and washed with the cold ethanol and dried. This was further
recrystallised from the methanol to obtain the desired product.
General microwave-assisted approach for the synthesis of indolin-2-one linked
chalcones.
A mixture of indolinꢀ2ꢀone (1.0 mmol) and substituted benzaldehyde 2 (1.1 mmol) was
dissolved in EtOH with catalytic amount of piperdine with continuous stirring at room
temperature. This mixture was then transferred to a Gꢀ10 process glass vial and tightly sealed
with teflon septum. After a preꢀstirring of 1 or 2 minutes, the vial was subjected to
microwave irradiation with the initial ramp time of 2 min at 60 °C. The temperature was then
raised to 140 °C with the holding time of 10 minutes. This solid was filtered and washed with
excess of ice cold methanol. This solid was pure enough for routine characterization.
General procedure for the synthesis of acetylinic linked chalcones
Indolinꢀ2ꢀone chalcone(1 equiv) was dissolved in 5 ml DMF followed by the addition of
anhydrous K CO (1.5 equiv/Indolinꢀ2ꢀone chalcone). The resulting suspension was stirred
2
3
for 30 min at room temperature which was then cooled to 0 °C. To this, propargyl bromide
1.3 equiv/substituted benzaldehydes) was subsequently added dropwise over a period of 10
(
min under stirring and the resulting mixture was allowed to stir at 25 °C for 16 h. The
reaction was monitored by TLC and on consumption of starting materials, quenched by ice
cold water resulting into the formation of precipitate. The precipitate so obtained was filtered,
washed with water and recrystallized from MeOH to afford the crystalline product in
excellent yield. The crude was then subjected to column chromatography with
EtOAc/Hexane 3:7 as eluent.
Synthesis of (E)-3-(4-fluorobenzylidene)-1-(prop-2-yn-1-yl)indolin-2-one (4a)

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Yellow solid, Yield: 94%, M.P.: 128ꢀ130 °C. Anal. Calcd. for: C18H12FNO: C, 77.97; H,
ꢀ1
4
.36; N, 5.05. Found: C, 77.96; H, 4.30; N, 5.14.21. IR (neat, cm ): 1177 (NꢀCH
2
), 1720
1
(
C=O), 2120 (C≡C), 3073(C=CꢀH), 3276 (C≡CꢀH). H NMR (400 MHz, CDCl
3
) δ 8.40 –
8.31 (m, 1H, H1), 7.84 (s, 1H, H5), 7.69 – 7.57 (m, 2H, H6, H7), 7.19 – 7.07 (m, 3H, H4, H8,
H9), 6.96 (t, J = 7.7 Hz, 2H, H2, H3), 4.62 (d, J = 2.7 Hz, 2H, ꢀNꢀCH ), 2.26 (t, J=2.4Hz,
2
1
3
1
H, ꢀC≡CH). C NMR (101 MHz, CDCl
3
, 25 °C) δ 168.4 (s), 145.9 (s), 129.4 (s), 125.0 (s),
122.5 (s), 121.6 (s), 120.9 (s), 120.1 (s), 118.9 (s), 113.2 (s), 108.8 (s), 77.2(s), 72.1 (s), 29.3
(s).
Synthesis of (E)-3-(2,4-dichlorobenzylidene)-1-(prop-2-yn-1-yl)indolin-2-one (4b)
Orange solid, Yield: 96%, M.P.: 140ꢀ142 °C. Anal. Calcd. for: C18 NO: C, 65.87; H,
), 1724 (C=O),
H11Cl
2
ꢀ
1
3
2
1
1
4
.38; N, 4.27. Found: C, 65.78; H, 3.25; N, 4.37. IR (neat, cm ): 1182 (NꢀCH
2
1
134 (C≡C), 3023(C=CꢀH), 3276 (C≡CꢀH). H NMR (400 MHz, CDCl
3
, 25 °C) δ 7.82 (d, J =
4.6 Hz, 1H, H5), 7.67 (d, J = 8.4 Hz, 1H, H1), 7.56 (d, J = 2.0 Hz, 1H, H4), 7.35 (dd, J =
3.8, 7.6 Hz, 3H, H6, H7, H8), 7.08 (d, J = 7.5 Hz, 1H, H2), 6.93 (t, J = 8.1 Hz, 1H, H3),
1
3
.62 (d, J = 2.5 Hz, 2H, ꢀNꢀCH
) δ 165.4 (s), 140.1 (s), 137.7 (s), 137.2 (s), 133.8 (s), 130.7 (s), 128.7 (s), 128.5 (s),
27.4 (s), 123.9 (s), 122.2 (s), 120.8 (s), 118.8 (s), 108.9 (s), 77.3 (s), 72.0 (s), 28.9 (s).
2
), 2.28 (t, J = 2.5 Hz, 1H, ꢀC≡CH). C NMR (101 MHz,
CDCl
3
1
Synthesis of (E)-3-(4-bromobenzylidene)-1-(prop-2-yn-1-yl)indolin-2-one (4c)
Red solid, Yield: 94%, M.P.: 135ꢀ137 °C. Anal. Calcd. for: C H BrNO: C, 63.92; H, 3.58;
18
12
ꢀ1
2
N, 4.14. Found: C, 63.88; H, 3.44; N, 4.21. IR (neat, cm ): 1222 (NꢀCH ), 1728 (C=O), 2128
1
(
C≡C), 3070(C=CꢀH), 3330 (C≡CꢀH). H NMR (400 MHz, CDCl
3
, 25 °C) δ 8.22 – 8.14 (m,
1H, H5), 7.77 (d, J = 22.2 Hz, 1H, H4), 7.70 – 7.51 (m, 3H, H1, H7, H8), 7.39 – 7.30 (m, 1H,
H6), 7.11 – 7.04 (m, 1H, H9), 6.93 (dt, J = 21.7, 8.2 Hz, 2H, H2, H3), 4.62 (d, J = 2.5 Hz,
1
3
2
H, ꢀNꢀCH ), 2.27 (t, J = 2.5 Hz, 1H, ꢀC≡CH). C NMR (101 MHz, CDCl ) δ 167.3 (s),
2
3

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1
1
36.2 (s), 135.9 (s), 133.7 (s), 133.4 (s), 132.0 (s), 131.6 (s), 130.8 (s), 130.1 (s), 123.1 (s),
22.9 (s), 122.3 (s), 122.0 (s), 110.2 (s), 109.4 (s), 77.2(s), 72.3 (s), 29.2 (s).
Synthesis of (E)-3-(4-nitrobenzylidene)-1-(prop-2-yn-1-yl)indolin-2-one (4d)
Dark yellow solid, Yield: 96%, M.P.: 110ꢀ112 °C. Anal. Calcd. for: C H N O : C, 71.05;
18
12
2
3
ꢀ1
H, 3.97; N, 9.21. Found: C, 77.22; H, 4.29; N, 5.45. IR (neat, cm ): 1219 (NꢀCH ), 1725
2
1
(
C=O), 2120 (C≡C), 3075(C=CꢀH), 3310 (C≡CꢀH). H NMR (400 MHz, CDCl
3
) δ 8.42 –
8
7
2
.11 (m, 4H, H6, H7, H8, H9), 8.09 (d, J = 8.2 Hz, 1H, H1), 7.83 (t, J = 10.8 Hz, 1H, H4),
.60 (d, J = 11.8 Hz, 1H, H2), 7.17ꢀ7.04 (m, 2H, H3, H5) 4.61 (d, J = 11.8 Hz, 2H, ꢀNCH ),
.27 (t, J = 8.1 Hz, 1H, C≡CH ). C NMR (101 MHz, CDCl ) δ 164.7 (s), 141.2 (s), 139.6
2
13
3
(
s), 133.9 (s), 133.8 (s), 132.3 (s), 130.9 (s), 130.5 (s), 130.3 (s), 129.9 (s), 129.1 (s), 124.3
s), 123.8 (s), 123.6 (s), 123.4 (s), 122.9, 122.7 (s), 122.5 (s), 119.8 (s), 109.3 (s), 77.3 (s),
(
72.3 (s), 29.1 (s).
Synthesis of (E)-3-(4-methoxybenzylidene)-1-(prop-2-yn-1-yl)indolin-2-one (4e)
Yellow solid, Yield: 95%, M.P.: 90ꢀ92 °C. Anal. Calcd. for: C H NO : C, 78.87; H, 5.23;
19
15
2
ꢀ1
N, 5.84. Found: C, 78.71; H, 5.29; N, 5.79. IR (neat, cm ): 1110 (NꢀCH ), 1720 (C=O), 2110
2
1
(
C≡C), 3055(C=CꢀH), 3330 (C≡CꢀH). H NMR (400 MHz, CDCl
3
, 25 °C) δ 8.41 (d, J = 8.9
Hz, 1H, H5), 7.89 – 7.77 (m, 2H, H4, H1), 7.68 (d, J = 8.6 Hz, 2H, H6, H9), 7.32 (t, J = 7.2
Hz, 1H, H2), 7.11 – 6.91 (m, 3H, H3, H7, H8), 4.63 (d, J = 2.5 Hz, 2H, ꢀNꢀCH ), 3.91 (s, 3H,
OCH ), 2.26 (t, J = 2.5 Hz, 1H, ꢀC≡CH). C NMR (101 MHz, CDCl ) δ 167.9 (s), 160.9 (s),
2
13
3
3
1
5
42.1 (s), 138.1 (s), 134.5 (s), 131.5 (s), 129.3 (s), 127.2 (s), 124.9 (s), 122.5 (s), 121.8 (d, J =
1.9 Hz), 121.6 (s), 113.9 (s), 109.1 (s), 77.2 (s), 72.1 (s), 55.4 (s), 29.2(s).

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O
O
NH
1
NH -NH H O
2
2.
2
NaOH
O
NH
Ar-CHO(a-e)
Piperdine 2 drops
Ar-CHO(a-e)
Piperdine 2 drops
2
Ar
Conventional, 720min,
reflux
MW, 140 °C, 15 min
O
NH
a-3e
3
Br
DMF, K CO3
2
Ar
N
CuBr(PPh3)3
CuBr(PPh3)3
O
THF, Et N
3
THF, Et N
o
3
O
1
00 C
O
o
6
0 C
Si
Si
4a-4e
N-
+ N-
O
N+
O
O
O
N
N
N
MW, 5min
Conventional, 240min
Ar
O
N
O
Si
O
O
N
N N
5a-5e
b
c
d
a
e
Cl
Ar
F
NO2
OCH3
Cl
Br
Scheme 1. General synthetic procedure of indolin chalcone siloxy based sensors both via
microwave as well as conventional heating method

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Traditional approach for the synthesis of indolin-2-one chalcone acetylene substituted
,2,3 triazole based organotriethoxysilanes
Indolinꢀ2ꢀone chalcone appended acetylene (ICAA) (1 equiv) was added to 1:1 THF/Et
1
3
N
solvent mixture taken in a twoꢀneck round bottomed flask and the mixture was stirred for 15.
min at room temperature. Then, slow addition of AzPTES (1 equiv/alkyne function) was
3 3
done followed by catalyst [CuBr(PPh ) ] (0.01 mmol/alkyne function) loading and the
mixture was stirred at 60 ºC for 240 mins. The reaction was then brought to room
temperature. The solvents were evaporated under reduced pressure subsequently addition of
hexane. The reaction mixture was then filtered and concentration of filtrate under reduced
pressure provided the viscous reddish orange silane in exceptional yield.
Microwave assisted synthesis of 1,2,3 triazole based organotriethoxysilanes
Compounds 5a-5e were prepared by oneꢀpot synthesis by irradiating the appropriate with ϒꢀ
azidopropyltriethoxysilane and appropriate catalyst with microwaves (Scheme 1). Table 1
compares time and reaction yield in THF:TEA (1:1) with those obtained by conventional
method. Our quantitative yields for traditional methods range from 71 to 96%. The
microwave synthesis provides an excellent alternative, with yields ranging between 86 to
98% at reaction times of 15 min; meaning a decrease factor in time of 16 compared to
traditional method.
Table 1. Optimization reaction conditions for the synthesis of silane 5a
Entry Catalyst Temperature Time Heating
Conversion
(%)
Loading
(Min) System
210 Oil bath 95%
1.
0.05mol 60 ºC

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2.
3.
4.
5.
6.
0.05mol 60 ºC
15
240
5
MW
98%
0.01mol 100 ºC
0.01mol 100 ºC
0.001mol 60 ºC
0.001mol 60 ºC
Oil bath 96%
MW
Oil bath 79%
MW 72%
100%
300
15
Synthesis
of
(E)-3-(4-fluorobenzylidene)-1-((1-(3-(triethoxysilyl)propyl)-1H-1,2,3-
triazol-4-yl)methyl)indolin-2-one (5a)
4 4
Dark yellow oil, Yield: 95%. Anal. Calcd. for: C27H33FN O Si: C, 61.81; H, 6.34; N, 10.68.
ꢀ1
Found: C, 61.86; H, 6.39; N, 10.69. IR (neat, cm ): 751, 1061 (SiꢀO), 949 (CꢀC), 1154(Oꢀ
1
CH
2
), 1251 (NꢀCH
400 MHz, CDCl
d, J = 6.4 Hz, 2H, H7, H8 ), 7.28 (s, 2H, H5, ꢀTzꢀH), 6.91 (d, J = 2.2 Hz, 1H, H6), 6.74 (d, J
10.9 Hz, 2H, H2, H3), 5.30 (s, 2H, ꢀNCH ꢀ), 4.41 (t, J = 7.1 Hz, 2H, N CH CH ), 3.83 (q,
H, ꢀOCH CH ), 2.21 – 1.87 (m, 2H, ꢀCCH Cꢀ), 1.40 – 1.03 (t, J = 6.9 Hz, 9H, OCH CH ),
2
), 1281 (CH
2
ꢀN), 1442 (CH
3
ꢀC), 1718(C=O), 2963 (C=CꢀH). H NMR
(
(
3
) δ 8.87 (s, 1H, H1), 8.56 (s, 1H, H4), 8.00 (d, J = 8.8 Hz, 1H, H9 ), 7.72
=
2
3
2
2
6
0
1
6
2
3
2
2
3
13
2 3
.70(t, J = 7.8 Hz, 2H, ꢀSiCH ꢀ). C NMR (101 MHz, CDCl , 25 °C) δ 168.3 (s), 145.9 (s),
29.4 (s), 125.1 (s), 122.5 (s), 121.6 (s), 120.9 (s), 120.3 (s), 118.9 (s), 113.2 (s), 108.8 (s),
2.6 (s), 58.6 (s), 52.6 (s), 24.2 (s), 18.3 (s), 7.5 (s).
Synthesis of (E)-3-(4-chloro-2-methylbenzylidene)-1-((1-(3-(triethoxysilyl)propyl)-1H-
,2,3-triazol-4-yl)methyl)indolin-2-one (5b)
1
Orange red oil, Yield: 94%. Anal. Calcd. for: C27
H
32Cl
2
N
4
O
4
Si: C, 56.34; H, 5.60; N, 9.73.
ꢀ1
Found: C, 56.34; H, 5.64; N, 9.75. IR (neat, cm ): 753, 1070 (SiꢀO), 956 (CꢀC), 1165(Oꢀ

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1
CH
2
), 1245 (NꢀCH
400 MHz, CDCl
d, J = 2.0 Hz, 1H, H4), 7.38 (s, 1H, ꢀTzꢀHꢀ), 7.37 – 7.32 (m, 3H, H6, H7, H8), 7.08 (d, J =
.5 Hz, 1H, H2), 6.93 (t, J = 8.1 Hz, 1H, H3), 5.30 (s, 2H, ꢀNCH ꢀ), 4.41 (t, J = 7.1 Hz, 2H,
2
), 1285 (CH
2
ꢀN), 1452 (CH
3
ꢀC), 1735 (C=O), 2970 (C=CꢀH). H NMR
(
(
3
, 25 °C) δ 7.82 (d, J = 14.6 Hz, 1H, H5), 7.67 (d, J = 8.4 Hz, 1H, H1), 7.56
7
2
N CH CH ), 3.83 (q, 6H, ꢀOCH CH ), 2.27 – 1.90 (m, 2H, ꢀCCH Cꢀ), 1.48 – 1.00 (t, J = 7.2
3
2
2
2
3
2
1
3
Hz, 9H, OCH
2
CH
s), 159.7 (s), 153.1 (s), 142.8 (s), 142.4 (s), 128.7 (s), 123.3 (s), 123.2 (s), 113.8 (s), 108.4
s), 100.2 (s), 62.2 (s), 58.6 (s), 52.6 (s), 24.2 (s), 18.3 (s), 7.5 (s).
3 2 3
), 0.75(t, J = 6.8 Hz, 2H, ꢀSiCH ꢀ). C NMR (101 MHz, CDCl ) δ 163.5
(
(
Synthesis
of
(E)-3-(4-bromobenzylidene)-1-((1-(3-(triethoxysilyl)propyl)-1H-1,2,3-
triazol-4-yl)methyl)indolin-2-one (5c)
4 4
Dark red oil, Yield: 96%. Anal. Calcd. for: C27H33BrN O Si: C, 55.38; H, 5.68; N, 9.57.
ꢀ1
Found: C, 55.36; H, 5.59; N, 9.53. IR (neat, cm ): 750, 1065 (SiꢀO), 959 (CꢀC), 1168, 1241
1
(
NꢀCH
2
), 1286 (CH
2
ꢀN), 1456 (CH
3
ꢀC), 1732 (C=O), 2979 (C=CꢀH). H NMR (400 MHz,
CDCl , 25 °C) δ 8.22 – 8.14 (m, 1H, H5), 7.77 (d, J = 22.2 Hz, 1H, H4), 7.70 – 7.51 (m, 4H,
3
H1, H6, H7, H8), 7.34(s, 1H, ꢀTzꢀHꢀ), 7.11 – 7.04 (m, 1H, H9), 6.93 (d, J = 21.7 Hz, 2H, H2,
H3), 5.30 (s, 2H, ꢀNCH
2
ꢀ), 4.41 (t, J = 7.1 Hz, 2H, N
.27 – 1.90 (m, 2H,ꢀCCH Cꢀ), 1.48 – 1.00 (t, J = 7.0 Hz 9H, OCH
ꢀ). C NMR (101 MHz, CDCl ) δ 158.2 (s), 153.1 (s), 142.6 (s), 138.3 (s), 134.4
3
CH
2
CH
2
), 3.83 (q, 6H, ꢀOCH
2 3
CH ),
2
2
2
2
CH ), 0.75 (t, J = 6.8 Hz,
3
1
3
H, ꢀSiCH
2
3
(s), 127.3 (s), 123.1 (s), 121.9 (s), 120.6 (s), 113.3 (s), 62.6 (s), 58.6 (s), 52.6 (s), 24.2 (s),
+
1
8.3 (s), 7.5 (s). MS: m/z 586.27.25 (M+H ).
Synthesis of (E)-3-(4-nitrobenzylidene)-1-((1-(3-(triethoxysilyl)propyl)-1H-1,2,3-triazol-
-yl)methyl)indolin-2-one (5d)
Yellowish orange oil, Yield: 94%. Anal. Calcd. for: C27
4
H
33
N
5
O
6
Si: C, 58.78; H, 6.03; N,
ꢀ1
1
2.69. Found: C, 58.81; H, 6.09; N, 12.80. IR (neat, cm ): 759, 1069 (SiꢀO), 950 (CꢀC),

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1
1
152(OꢀCH
NMR (400 MHz, CDCl
H1), 7.83 (t, J = 10.8 Hz, 1H, H4), 7.40 (s, 1H, ꢀTzꢀHꢀ), 7.60 (d, J = 11.8 Hz, 1H, H2), 7.17ꢀ
2
), 1241 (NꢀCH
2
), 1282 (CH
2
ꢀN), 1446 (CH
3
ꢀC), 1732 (C=O), 2956 (C=CꢀH). H
3
) δ 8.42 – 8.11 (m, 4H, H6, H7, H8, H9), 8.09 (d, J = 8.2 Hz, 1H,
7
7
.04 (m, 2H, H3, H5), 5.34 (s, 2H, ꢀNCH ꢀ), 4.41 (t, J = 7.2 Hz, 2H, N CH CH ), 3.83 (q, J =
2 3 2 2
.0 Hz, 6H, ꢀOCH CH ), 2.06 (m, 2H, ꢀCCH Cꢀ), 1.23 (t, J = 7.0 Hz, 9H, OCH CH ), 0.78
2
3
2
2
3
1
3
(
t, J = 6.8 Hz, 2H, ꢀSiCH
2
ꢀ). C NMR (101 MHz, CDCl
38.2 (s), 132.9 (s), 132.1 (s), 132.0 (s), 130.3 (s), 128.6 (s), 128.4 (s), 122.9 (s), 122.3 (s),
20.1 (s), 113.4 (s), 62.2 (s), 58.5 (s), 52.6 (s), 24.2 (s), 18.3 (s), 7.5 (s). MS: m/z 595.30 (M+
3
) δ 158.8 (s), 156.5 (s), 143.3 (s),
1
1
+
+
K + 4H ).
Synthesis of (E)-3-(4-methoxybenzylidene)-1-((1-(3-(triethoxysilyl)propyl)-1H-1,2,3-
triazol-4-yl)methyl)indolin-2-one (5e)
36 4 5
Dark yellow oil, Yield: 96%. Anal. Calcd. for: C28H N O Si: C, 62.66; H, 6.76; N, 10.44.
ꢀ1
Found: C, 62.71; H, 6.79; N, 10.89. IR (neat, cm ): 758, 1078 (SiꢀO), 949 (CꢀC), 1158(Oꢀ
1
CH ), 1246 (NꢀCH ), 1265 (CH ꢀN),1459 (CH ꢀC), 1636 (C=N), 2962 (C≡CꢀH). H NMR
2
2
2
3
(
400 MHz, CDCl ) δ 8.41 (d, J = 8.9 Hz, 1H, H5), 7.89 – 7.77 (m, 2H, H4, H1), 7.68 (d, J =
3
8
.6 Hz, 2H, H6, H9), 7.56 (s, 1H, TzꢀH) 7.32 (t, J = 7.2 Hz, 1H, H2), 7.11 – 6.91 (m, 3H, H3,
H7, H8), 3.91 (s, 3H, OCH ), δ 5.30 (s, 1H, ꢀNCH ꢀ), 4.41 (t, J = 7.1 Hz, 2H, N CH CH ),
.83 (q, 6H, OCH CH ), 2.30 – 1.79 (m, 2H, ꢀCCH Cꢀ), 1.45 – 0.98 (t, J = 6.9 Hz, 9H,
OCH CH ), 0.78 (t, J = 7.1 Hz, 2H, ꢀSiCH ꢀ). C NMR (101 MHz, CDCl ) δ 158.2 (s), 153.1
3
2
3
2
2
3
2
3
2
1
3
2
3
2
3
(s), 142.6 (s), 138.3 (s), 134.4 (s), 127.3 (s), 123.1 (s), 121.9 (s), 120.6 (s), 113.3 (s), 62.6 (s),
+
+
5
8.6 (s), 55.4(s), 52.6 (s), 24.2 (s), 18.3 (s), 7.5 (s). MS: m/z 579.19 (M+ K + 4H ).
Conclusion
In summary, we have designed and synthesized a highly selective and sensitive chemosensor
following microwave assisted approach using 2+3 cycloaddition reaction of ICAA and ϒꢀ
2
+
azidopropyltriethoxysilane for the detection of Cu . The host guest complex between chemo

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2
+
sensor and Cu was stable in neutral conditions. BꢀH plot discloses 1:1 ratio between the
2+
chemosensor and Cu . The interactions of chemosensor were gauged against different metal
ions solutions in acetonitrile with the help of UVꢀvisible spectroscopy. Results showed that
2+
chemosensor selectively detect Cu even in the presence of other metal ions. Proposed
systems can be used for monitoring of samples of biological and ecological relevance.
Supporting Information
1
13
H NMR, C NMR and Mass spectra of acetylenic indolinꢀ2ꢀone appended chalcones
triethoxysilanes as characterization data.
Acknowledgements
The authors are thankful to UGC Project (MRPꢀMAJORꢀCHEMꢀ2013ꢀ26532), DSTꢀPURSE
and DSTꢀSERB for providing financial support.
References
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Page 25 of 26
New Journal of Chemistry
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DOI: 10.1039/C8NJ02884B
Chalcone scaffolds as photo functional hybrid material of indolin-2-one functionalized
2
+
siloxy framework for optical sensing of Cu
a, *
a
b
a
a
Gurjaspreet Singh , Pooja Kalra , Aanchal Arora , Akshpreet Singh , Geetika Sharma ,
a
a
Sanchita , Pinky Satija
a
Department of Chemistry and Centre of Advanced Studies, Panjab University, Chandigarh,
1
60014, India
b
Khalsa College for Women, Civil Lines, Ludhiana, Punjab, 143002, India
*
Corresponding Author
Dr. Gurjaspreet Singh
Associate Professor
Department of Chemistry and Centre of Advanced Studies
Panjab University, Chandigarh, India
+91-0172-2534428
Email: gjpsingh@pu.ac.in

New Journal of Chemistry
Page 26 of 26
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DOI: 10.1039/C8NJ02884B
MW
CONVENTIONAL
2+
Cu
The present article is about synthesis of indolin-2-one chalcone based photo functional hybrid for
2
+
selective and sensitive detection of Cu .