Synthesis, structure, fluorescent property, and antibacterial activity of new Cd(II) metal complex based on multidentate Schiff base ligand N,N′-Bis(3-methoxysalicylidenimino)-1,3-diaminopropane

Article abstract of DOI:10.1016/j.molstruc.2017.01.002

The sequential reaction of a multisite coordinating compartmental ligand N,N′-Bis(3-methoxysalicylidenimino)-1,3-diaminopropane (H₂L¹) with Cd(OAc)₂ followed by the addition of NaCl in a 2:3:2 stoichiometric ratio affords

Full text of DOI:10.1016/j.molstruc.2017.01.002

Accepted Manuscript
Synthesis, structure, fluorescent property, and antibacterial activity of new
Cd(II) metal complex based on multidentate Schiff base ligand N,N′-Bis(3-
methoxysalicylidenimino)-1,3-diaminopropane
Dhrubajyoti Majumdar, Sourav Das, Jayanta Kumar Biswas, Monojit Mondal
PII:
S0022-2860(17)30002-9
10.1016/j.molstruc.2017.01.002
MOLSTR 23307
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 19 October 2016
Revised Date: 31 December 2016
Accepted Date: 1 January 2017
Please cite this article as: D. Majumdar, S. Das, J.K. Biswas, M. Mondal, Synthesis, structure,
fluorescent property, and antibacterial activity of new Cd(II) metal complex based on multidentate Schiff
base ligand N,N′-Bis(3-methoxysalicylidenimino)-1,3-diaminopropane, Journal of Molecular Structure
(2017), doi: 10.1016/j.molstruc.2017.01.002.
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Graphical Abstract

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Synthesis, structure, fluorescent property, and antibacterial activity of new
Cd(II) metal complex based on multidentate Schiff base ligand N,N'-Bis(3-
methoxysalicylidenimino)-1,3-diaminopropane
Dhrubajyoti Majumdara,*, Sourav Dasb,*, Jayanta Kumar Biswasc, Monojit Mondalc
a,*Department of Chemistry; Tamralipta Mahavidyalaya, Tamluk-721636, West Bengal, India
b,*Department of Chemistry; Institute of Infrastructure Technology Research and Management;
Near Khokhara Circle, Maninagar East, Ahmedabad-380026, Gujarat, India
cDepartment of Ecological Studies, University of Kalyani, Kalyani-741235 , West Bengal, India
AUTHOR EMAIL ADDRESS: dmajumdar30@gmail.com

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Abstract
The sequential reaction of a multisite coordinating compartmental ligand N,N'-Bis(3-
methoxysalicylidenimino)-1,3-diaminopropane (H2L1) with Cd(OAc)2 followed by the addition
of NaCl in a 2:3:2 stoichiometric ratio affords homometallic trinuclear Cd(II) coordination
compound [Cd3(L1)2(Cl)2] (1). The complex 1 has been thoroughly characterized by common
elemental analysis (CHN), FT-IR and UV-Vis spectroscopy. Single crystal X-ray diffraction was
also performed to determine the complete structure of complex 1. X-ray diffraction studies reveal
that the molecular complex comprises a linear tri-nuclear ensemble of cadmium metal ions,
which is further supported by the concerted coordination action of two dianionic [L1]2– ligands
along with two monodentate Cl- ligands. The central Cd(II) ion is attached to the terminal Cd(II)
ions through two phenoxide bridging groups of the fully deprotonated ligands [L1]2–. This
arrangement leads to two neighboring four membered Cd2O2 rings. The terminal Cd(II) ions are
penta-coordinated (2N, 2O, Cl) in a distorted square pyramidal geometry and central Cd(II) ion
attained distorted trigonal prismatic geometry through six oxygen atoms coordination from
ligands. Tri-nuclear Cd(II) complex 1 display intraligand (π—π*) fluorescence in DMSO
solution at room temperature. The fluorescence properties of complex 1 as well as the respective
di-compartmental Schiff base ligand (H2L1) have been investigated in DMSO solvent at room
temperature with a comparative approach. Result confirmed that complex 1 is highly
fluorescence active mediated due to “chelation enhanced fluorescence” [CHEF] but Schiff base
ligand (H2L1) is fluorescence silent. The antibacterial efficacy of complex 1 was further
investigated against some important Gram-positive and Gram-negative bacteria.
Keywords: Cd(II) trinuclear complex, X-ray crystal structure, fluorescence properties, week
supramolecular interaction, Antimicrobial activity.

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1. Introduction
Over the past few decades, the complexation behavior of group 12 metal ions (Zn, Hg or Cd) in
presence multidentate Schiff base ligands have rigorously studied vital research area in the field
of coordination chemistry [1-5]. The molecular metal ensembles derived from Schiff base
ligands and group 12 metal ions are of substantial contemporary interest considering versatile
functional behaviors, intriguing structural motifs [6-10] and optoclectronics properties [11-
13].However, from the synthetic point of view the major confront is to design suitable ligands
which can assemble metal ions together. Multi-metal assemblies of varying nuclearity are often
synthesized and crystallized from common one-pot reaction from a pool of ingredients like
appropriate molar ratios of metal salts, suitable multi-compartmental Schiff base ligands, in one
step which affords many diverse structural topologies [14,15]. Hence Schiff base on account of
its endearing popularity and versatility towards wide range of complex formations, many
inquisitive chemists got interested to their complex formation. In the 19th century [1864] Prof.
Sir Hugo Schiff opened the beautiful research gate in the field of coordination chemistry after his
novel discovery of Schiff base [16]. Recently many inquisitive inorganic chemists carry out their
research work by using Schiff base because of their easily preparation, wide structural varieties,
varied denticities and ease of tunability in ligand steric or electronic properties. Hence in the
current research scenario, Schiff base complex formation have been extensively studied on
account of their different mode of applications, e.g. catalysis[17-19], magnetism [20,21],
synthons for crystal engineering and most popular materials chemistry[22-24]. Group 12 metal
ions Cd and its congeners metal Zn, Hg are always biologically harmful, yet recently it has been
found that Cd(II) ion can potentially serve catalytic center in a newly discovered carbonic
anhydrase [25]. In Cd(II) complexes, the metal centre always enable a diverse range of

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coordination geometries and coordination numbers due to lack of crystal field stabilization
energy as well as imposed ligands steric demands from the Schiff base ligands. Thus a balance
between bonding energies and repulsion created by inserted Schiff base ligands determine the
overall flexibility in coordination numbers [26-28]. Since Cd(II) ion has no optical spectroscopic
signature due to its closed–shell 3d10 configuration, luminescence behavior of Cd(II) metal is
enhanced due to ‘chelation concept’ developed by metal and ligand donor centers strong binding
ability. Additionally d10 metal ions like Zn(II) & Cd(II) when associated with Schiff base
ligands that already conjugated with aromatic π rings favour the development of sensitive
fluorescent active property[29-33]. A complete literature survey reveals that di-compartmental
Schiff base ligand, N,N’-bis(2-hydroxyacetophenone)-1,3-diaminopropane where only one
phenoxo-bridged tri-nuclear copper(II) complex has been reported so far [34,35]. A plenty of
examples of tri-nuclear Cd(II) thiocyanato or azido bridging complexes [36,37] are well known
but on contrary Cd-Cl terminal linking tri-nuclear complexes are scare. This Literature survey
work stems from our interest to investigate the coordination behaviors of endeaviour Schiff base
towards Cd(II) metal ion in concert with Cl- ion as monodentate ligating fashion.
In the present research study, we have synthesized N2O4 donor di-compartmental Schiff base
ligand (H2L1) by the condensation of one equivalent 1,3-diamines and two equivalent 3-
methoxysalicylaldehyde (Scheme1). Using the Schiff base ligand we have successfully
synthesized a new tri-nuclear ensemble Cd(II) complex [Cd3(L1)2(Cl)2] (1) . Our research interest
in the current work is to observe Cd(II) metal ions coordination behavior towards the respective
Schiff base ligand using NaCl as Cl- spacer. The synthetic details of Schiff base ligand, its
respective complex 1, their spectral characterization, X-ray crystal structure, details fluorescence
and antibacterial study have been reported in this work.

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Scheme 1: Synthesis of the ligand (H2L1)
2. Experimental
2.1. General remarks and physical measurement
2.1.1. Materials
All chemicals were of reagent grade, purchased from commercial sources and used as received
without further purification. High purity 3-methoxysalicylaldehyde was purchased from Sigma
Aldrich Company, USA. 1,3-Diaminopropane was also purchased from the same company.
Cadmium(II) acetate and Sodium chloride were purchased from E. Merck, India. The Schiff
base (H2L1 = N,N’-Bis(3-methoxysalicylidenimino)-1,3-diaminopropane) has been prepared by
condensation of a 1:2 M ratio of 1,3-diaminopropane and 3-methoxysalicylaldehyde following a
reported method [38]. All other chemicals and solvent methanol used were AR grade. The total
synthetic reactions for research purpose and work-up were done in open air condition.
2.1.2. Instrumentation
Elemental analyses (carbon, hydrogen and nitrogen) of the Scihff base (H2L1) and the metal
Cd(II) complex 1 were determined with a Perkin–Elmer CHN analyzer 2400. IR spectra (KBr
pellet, 400–4000 cm-1) were recorded on a Perkin–Elmer model 883 infrared spectrophotometer.
The electronic UV-Vis spectra of the Cd(II) complex 1 and respective Schiff base ligand in
1
organic solvent DMSO were recorded on a Hitachi model U-3501 spectrophometer. The H
NMR spectra of novel Schiff base (H2L1) were recorded on Bruker 300MHz FT-NMR

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spectrophotometer using trimethylsilane as internal standard in CDCl3 solvent. All spectra were
corrected for the instrumental functions. Perkin-Elmer LS50B spectrofluorimeter model was
used for the fluorescence measurements of tri-nuclear Cd(II) complex 1 and Schiff base ligand
(H2L1) at room temperature(298K). The solutions of Schiff base ligand (H2L1) and Cd(II)
complex 1 were prepared in DMSO solvent.
2.3. X-ray Crystallography
The crystal data for the compounds have been collected on a Bruker SMART CCD diffractometer
(MoKα radiation, λ = 0.71073 Å). The program SMART[39] was used for collecting frames of
data, indexing reflections, and determining lattice parameters, SAINT [39] for integration of the
intensity of reflections and scaling, SADABS [40] for absorption correction, and SHELXTL
[41,42] for space group and structure determination and least-squares refinements on F2. The
crystal structures were solved and refined by full-matrix least-squares methods against F2 by
using the program SHELXL-2014 [43] using Olex-2 software [44]. All the non-hydrogen atoms
were refined with anisotropic displacement parameters. Hydrogen positions were fixed at
calculated positions and refined isotropically. Different crystallographic figures were generated
using Diamond-3.1 software [45]. A summary of the crystallographic data and structure
refinement parameters of tri-nuclear Cd(II) complex 1 is given in Table 1. Crystallographic data
(excluding structure factors) for the structures in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC 1495264.
Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, U.K.: http://www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi, e-mail:
data_request@ccdc.cam.ac.uk, or fax: +44 1223 336033.

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Table 1. Crystal Data and Structure Refinement Parameters of Complex 1
Formula
M/g
C38H40Cd3Cl2N4O8
1088.84
Crystal system
Space group
a/Å
monoclinic
P21/c
19.433(4)
b/Å
8.9050(18)
c/Å
23.357(5)
β (°)
100.61(3)
3972.8(14)
V/Å3
Z
4
ρc/g cm-3
ꢀ/mm-1
1.820
1.782
F(000)
2152
Cryst size (mm3)
θ range (deg)
Limiting indices
0.054 × 0.038 × 0.012
4.464 to 58.26
-26 ≤ h ≤ 26
-12 ≤ k ≤ 12
-31 ≤ l ≤ 31
Reflns collected
Ind reflns
65644
10584 [Rint = 0.1061, Rsigma = 0.0766]
99
Completeness to θ (%)
Refinement method
Data/restraints/ parameters
Goodness-of-fit on F2
Final R indices
Full-matrix-block least-squares on F2
10584/0/500
1.034
R1 = 0.0505
[I > 2θ(I)]
wR2 = 0.1028
R indices (all data)
R1 = 0.0777
wR2 = 0.1133
1.07 and -0.92
Largest diff. peak and hole(e ·Å-3)
2.1.3. Experimental of antimicrobial activity
In vitro antimicrobial potentiality of complex 1 was analyzed against four Gram negative
bacterial strains viz. Escherichia coli K12, Salmonella enterica ser. typhi SRC, Proteus vulgaris
OX19 and Enterobacter aerogenes 10102, and one Gram positive bacterial strain viz. Bacillus
subtilis 6633, which were obtained from Microbial Type Culture Collection and Gene Bank
(MTCC), Institute of Microbial Technology, Chandigarh, India and Department of

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Microbiology, University of Kalyani, West Bengal, India. Initially complex 1 was dissolved in
dimethyl sulfoxide (DMSO) and the final concentration of DMSO was always maintained below
1%.As the reference material Amoxicillin was used (Saha et al., 2014) [46]. Luria-Bertani (LB)
medium (Modified) was used for antimicrobial analysis and minimum inhibitory concentrations
(MIC) of complex 1 against the tested strains were determined as per NCCLS protocol (NCCLS,
1993) [47]. Different concentrations of complex 1 were prepared and administered in the
sterilized LB broth. Following inoculation (1%) of the overnight culture the tubes were incubated
at 37°C for 24 hours. Turbidity in the broth was measured by UV-VIS spectrophotometer at 600
nm to identify the MIC. Bacterial susceptibility of the complex was experimented using agar
well diffusion method and the potentiality was determined by measuring the growth inhibition
zone diameter (mm) (Bauer et al., 1966) [48]. Bacterial growth kinetics in presence of complex 1
was examined against four bacterial strains (Bacillus subtilis 6633, Enterobacter aerogenes
10102, Proteus vulgaris OX19 and Salmonella enterica ser. typhi SRC).
2.2. Synthesis
2.2.1. Synthesis of Schiff base (H2L1)
The Schiff base ligand (H2L1) has been synthesized and characterized using literature method
[38]. Yield: (90%), Anal. Calc. for C19H22N2O4: C, 66.65; H, 6.48; N, 8.18 Found: C, 6.71; H,
6.42; N, 8.08%. IR (KBr, νmax/cm-1): ν(C=N) 1641, ν(C-Ophenolic) 1254, ν(O-H) 3449, UV-vis
1
(λmax/ nm): 258, 398 nm. H NMR for H2L1 (δ, 300MHz): 2.11(t, J=6.45, 2H8), 3.74 (t, J=8.1,
2H7), 3.91 (s, 3H1), 6.79-6.95(m, 1H2, 1H3, 1H4), 8.37 (s, 1H5), 13.94 (s, 1H6).
2.2.2. Synthesis of complex 1 [Cd3 (L1)2 (Cl)2]

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Schiff base (H2L1) (0.342 g, 1 mmol) in methanol (15mL) was added dropwise to a solution of
Cadmium acetate dihydrate (0.345 g, 1.5 mmol) of the same solvent (25mL) and stirred for 10
minutes. To the resulting deep yellow solution, aqueous solution (5mL) of NaCl (0.05844 g,
1mmol) was added slowly with constant stirring for 4 hr. The yellow coloured solution was
additionally refluxed for 15 min at 700C and the resulting yellow filtrate was kept in refrigerator
for crystallization by slow evaporation. After 10 days yellow coloured single crystal suitable for
X-ray crystallography was obtained. Deep yellow crystal was isolated by filtration and air dried.
Yield: 0.382 g (70%) Anal. Calc. for C38H40Cd3Cl2N4O8: C, 41.92; H, 3.70; N, 5.15 Found: C,
41.90; H, 3.70; N, 5.14 %. IR (KBr, νmax/cm-1): ν(C=N) 1627, ν(O-H) 3442, ν(C-H) 2931-2849 ,
ν(Cd-N) 457, ν(Cd-O) 400, UV-vis (λmax/ nm): 266 nm & 348 nm.
3. Results and discussion
3.1. Tri-nuclear Cd(II) complex (1) synthesis and characterization
We have unambiguously used one-pot synthetic methodology to obtain tri-nuclear Cd(II)
complex 1, where 3:2:2 M ratio of the respective Cadmium(II) acetate dehydrate, di-
compartmental Schiff base (H2L1) and Sodium chloride(self-assembly) from methanolic solvent
medium at room temperature yield the Cd(II) yellow colored complex 1. The synthetic reaction
for yellow coloured complex 1 is depicted in scheme 2.

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Scheme 2: Synthetic scheme for the preparation of metal complex 1
The synthesized new Cd(II) complex 1 has been characterized by different well known
microanalytical (C, H and N), spectroscopic and other well known physicochemical results.
Different microanalytical data are in good conformity with the Cd(II) complex formulation. Our
synthesized yellow Cd(II) complex 1 is stable over long period of time in powdered form as
well as crystalline states and readily soluble in organic solvent like DMSO, DMF, CH3CN, but
insoluble in water. Several week bands in the range 2931-2849 cm-1 are strongly observed in
complex 1, this is mainly assignable to the aliphatic C-H stretching vibration [49].The infrared
spectra of complex 1 is consistent with the structural data given in Figure S1 (see Supplementary
material). An intense strong band at 1630 cm-1 for complex 1 is shifted considerably towards
lower frequencies compared to that of the free Schiff base ligand (H2L1) indicating coordination
of the imino nitrogen atom with the Cd(II) metal centers [50]. Schiff base ligand coordination to
Cd(II) metal center is substantiated by prominent bands appearing at 457 and 400 cm-1 which can
be attributed to ν(Cd-N) and ν(Cd-O) respectively in complex 1. Yellow coloured DMSO
solution at room temperature of tri-nuclear Cd(II) complex exhibit ligand–based transition at
266 nm and 348 nm presumably due to n→π* or π→π* transitions [51,52]. The UV–visible
absorption spectrum is depicted in Figure S2 (see Supplementary material).

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3.2. X-ray Crystal Structure of [Cd3 (L1)2(Cl)2] (1)
Single-crystal X-ray diffraction studies reveal that 1 is neutral complex that crystallize in the the
monoclinc system in P21/c space group with Z = 4. A perspective view of the complex 1 is
depicted in Figure 1. Selected bond parameters of 1 are summarized in the Table S1 (See
Supplementary material).
µ2 – η1: η2: η1: η1: η2
Scheme 3. Binding mode of the ligand ([L]2–)
The homometallic complex possesses a trinuclear [Cd3(ꢀ2-O)4]3+core (Figure 1 and 3) which is
assembled as a result of the cumulative coordination action of two doubly deprotonated [L]2-
ligands. The fully deprotonated ligand has six potential coordination site but its uses its five
potential coordination site to hold together two Cd(II) ions in a ꢀ2 – η1: η2: η1: η1: η2 fashion
(Scheme 3). Each [L]2- uses two ꢀ-phenolate oxygen, two imino nitrogen, and the one oxygen
atoms of the methoxy (-OMe) groups. Interestingly, one -OMe group of the ligand remains non-
coordinating (Scheme 2 and 3). In the trinuclear ensemble, each of the two terminal Cd(II)
centers is surrounded by a [L]2- ligand and is bound by two phenolate oxygen atoms (O2 and
O3), two imino nitrogen atoms (N2 and N1). Apart from these in order to satisfy the charge and
coordination requirements, a chloride anion coordinate the terminal Cd(II) ion in a monodentate
fashion generating a CdO2N2Cl coordinating environment. So, the terminal Cd(II) center display

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distorted square pyramidal coordination sphere (Figure 2). The geometry distortion information
in favor of complex 1 can be obtained from structural index or addison parameter ґ[53] which
represents the relative amount of trigonally in the crystal structures and for square pyramid, ґ =
0; trigonal bipyramid, ґ =1; ґ = (α-β)/60º, where α and β are the two largest angles around the
metalions Cd1 & Cd3 .The calculated Addison parameter ґ are 0.0635 & 0.175 for Cd1, Cd3
that confirmed distorted square pyramidal geometry around the metal centers Cd1 & Cd3.
Figure 1. ORTEP diagram of 1 with the atom numbering scheme (non-hydrogen atoms have
been shown at 50% ellipsoid probability).

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b)
a)
Figure 2. (a) Distorted square pyramidal and (b) distorted trigonal prismatic geometry around
Cd(II) ion.
An all-oxygen coordination sphere is achieved around the central Cd(II) ion which has an overall
6O coordination environment in a distorted trigonal prismatic geometry (Figure 2). Interestingly,
here it is important to mention that the non-coordinating -OMe group of the ligand display strong
of van der waals interaction with the central Cd(II) ion with a average bond distance around
2.721(3) Å (Figure 1). All the two [L]2- ligands present in the complex are involved in binding
of central Cd(II) centre. In addition to the four phenolate oxygen atoms (O2, O3, O6 and O7) two
oxygen atoms from the methoxy group (O1 and O5) are also involved in coordination. Each of

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the terminal Cd(II) and the central Cd(II) centers are bridged by two phenolate oxygen atoms
generating two 4-membered slightly non-planar Cd2(O)2 rings which bisect each other with an
angle of 82.36(9)° with respect to each other (Figure 3). Also, as result of the bridging phenolate
coordination the three metal ions are placed in a almost linear arrangement with a Cd1-Cd2-Cd3
bond angle of 174.31(2)°. The average inter CdII-CdII distance is 3.58(1) Å.
Figure 3. The trinuclear core of 1 showing two four-membered Cd2(O)2 rings at an angle of ~
82°.
An inspection of metric parameter reveals that the Cd–Ophenolate bond lengths are in the range of
~2.220–2.279 Å. On the other hand, Cd–Omethoxy and Cd-Cl bond lengths are moderately larger
than previous one and falls in the range of 2.458-2.489Å and 2.419-2.428 Å respectively. The
imino-nitrogen of the ligand binds with CdII ion with a distance of 2.250–2.285 Å. The Cd–O–
Cd angles lie in narrow ranges: 104.92– 106.26o (See Supplementary material).

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Figure 4. Neighbouring [Cd]3 trinuclear array are connected by 2D-hydrogen bonding network
along the ac plane.
Complex 1 is involved extensive with intermolecular C–H…..Cl interactions. A two-dimensional
hydrogen bonding network is seen along the ac plane where each trinuclear unit inteacts with
five neighbouring molecules through two coordinating Cl- ions with terminal metal ions (Figure
4). The bond parameters associated with the intermolecular hydrogen bonding are given in Table
S2 (See Supplementary material).

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3.3. Luminescence behavior of complex 1
We have studied fluorescence properties individually for Schiff base ligand (H2L1) and complex
1 to find out the fluorescence silent or active nature since fluorescence active property of
complex 1 opens up the new possibility of opportunity for photochemical applications [54-60].
Hence for this reason fluorescence properties of Schiff base ligand and its respective Cd(II)
complex 1 were studied at room temperature (298 K) in DMSO solvent. A Complete Analysis
reveals that Schiff base ligand exhibit emission at 390 nm while complex 1 shows emission at
462 nm upon excitation at 349 nm (Figure 5 and Table 2). Since Cd(II) ion has no optical
spectroscopic signature due to its closed–shell 3d10 configuration, hence Cd(II) is very difficult
to oxidize or reduce. Therefore fluorescence emission originating mainly from metal-centered
MLCT/LMCT excited states is not expected for complex 1. Thus for complex 1 emission is
tentatively assigned due to intraligand (π→π*) fluorescence. From Figure 5, we observed that
complex 1 fluorescence intensity is higher than that of free Schiff base ligand. The red shift as
well as greater intensity of complex 1 is presumably due to the conformational rigidity of the
ligand upon complexation or strong coordination with Schiff base (N,O) donor ligand [61-64].
The question comes out our minds that why complex1 fluorescence intensity is higher than that
of free Schiff base ligand. It is best way to explain such fact that on the basis of “chelation
mediated fluorescence intensity”. Normally Zn(II), Cd(II) metal ions enhance or quench
fluorescence emission in presence Schiff base ligand that contains aromatic π cloud ring system
and ligand donor centers nitrogen, oxygen are selectively bonded with respective metals.
Quenching of metal ions in presence of Schiff base ligand during complex formation via
different donor center (N, O) is a rather common fact which is explained in a lucid manner by a
process like magnetic perturbation, redox activity and electronic energy transfer. In the absence

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of suitable metal ions fluorescence property of the ligand is probably quenched by the occurrence
of photo induced electron transfer (PET) process due to presence of ligand donor atoms N, O
nonbonding electrons pairs. Such PET process is prevented by the Schiff base ligands when its
nonbonding electron pairs of donor centers N, O gets stable complexed with Cd(II) metal center.
The overall process is referred as “chelation enhanced fluorescence intensity”. Due to the
chelation effect of Cd(II) metal ion with Schiff base ligand (H2L1) donor centers nitrogen or
oxygen increases the rigidity of the ligand and thus reduces the loss of energy by thermal
vibrational decay[65].
Table 2. Photophysical parameters of Schiff base ligand (H2L1) and complex 1 in DMSO solvent
at room temperature 298 K.
Compound
Schiff base ligand
(H2L1)
Abssorption (λmax), nm Excitation (λmax), nm Emission (λmax), nm
258 & 398 nm
332 nm
390 nm
Complex 1
266 & 348 nm
348 nm
462 nm

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Figure 5. Fluoresecence spectra of Schiff base ligand (H2L1) & complex 1 in DMSO solution at
298 K.
3.4. Antimicrobial screening of complex 1
This study exhibited that the synthesized complex 1 has the potentiality to inhibit bacterial
growth. MIC values and growth inhibition zone diameters of the tested bacterial strains for the
complex are presented in Table 3. The complex 1 showed a wide range of antibacterial activity
and it had the similar antibacterial potentiality against both Gram positive and Gram negative
bacteria. Among the tested strains B. subtilis 6633 and P. vulgaris OX19 were most susceptible
to MIC value of 60µg/mL, where as E. aerogenes 10102 was less susceptible to MIC value of
200µg/mL against the complex. The MIC values of the complex 1 were lower than the MIC
values of Amoxicillin in case of P. vulgaris OX19 and E. aerogenes 10102. From this study it
can be concluded that the complex 1 has broad spectrum of antibacterial activity. The growth
kinetics analysis showed that the complex has promising potentiality to restrict bacterial growth

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as a bacteriostatic agent, which is illustrated in the in vitro growth curve (Figure 6) of four
bacterial strains (Bacillus subtilis 6633, Enterobacter aerogenes 10102, Proteus vulgaris OX19
and Salmonella enterica ser. typhi SRC).
Table 3. MIC (µg/mL) and corresponding growth inhibition zone diameter (mm) of complex 1
and Amoxicillin against the tested bacterial strains. Amoxicillin was used as standard
antimicrobial agent. All data were taken in triplicate.
Complex 1
Amoxicillin
Organisms
MIC
Zone of
MIC
Zone of
(µg/mL)
Inhibition (mm)
8.5 ± 0.5
(µg/mL)
30
Inhibition (mm)
B. subtilis 6633
E. aerogenes 10102
E. coli K12
60
200
140
60
8.4 ± 0.3
8.5 ± 0.4
12.3 ± 0.2
8.0 ± 0.3
9.1 ± 0.3
6.2 ± 0.3
280
10
5.7 ± 0.2
P. vulgaris OX19
S. typhi SRC
9.7 ± 0.3
125
35
130
5.5 ± 0.5

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0.6
0.4
0.2
0
B. subtilis 6633 Control
B. subtilis 6633+Complex (1)
1.6
E. aerogenes 10102 Control
E. aerogenes 10102+Complex (1)
1.2
0.8
0.4
0
0
2
4
6
8
10
12
14
16
18
20
0
2
4
6
8
10
12
14
16
18
20
(b)
Time (Hour)
(a)
Time (Hour)
0.8
0.6
0.4
0.2
P. vulgaris OX19 control
P. vulgaris OX19+Complex (1)
1
S. typhi SRC control
S. typhi SRC+Complex (1)
0.8
0.6
0.4
0.2
0
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16
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20
0
(d)
Time (Hour)
0
2
4
6
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Time (Hour)
(c)
Figure 6. Time dependent in vitro growth curves of (a) Bacillus subtilis 6633, (b) Enterobacter
aerogenes 10102, (c) Proteus vulgaris OX19 and (d) Salmonella enterica ser. typhi SRC
subjected to complex 1. (All data were taken in triplicate and error bars show standard
deviations).
4. Concluding remarks
The synthesis and structural characterization of homometallic trinuclear linear complex
[Cd3(L1)2(Cl)2] (1) was described. The homometallic complex consists a trinuclear [Cd3(ꢀ2-
O)4]3+core which is assembled as a result of the cumulative coordination action of two doubly
deprotonated [L]2- ligands. The central cadmium attached by µ-phenolato-oxygen & methoxy

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group oxygen atoms. Terminal Cd(II) metal bonded with µ-phenolato-oxygen & imino-nitrogen
atoms in addition with monodentate Cl- ions. Thus central Cd(II) attained distorted trigonal
prismatic geometry but other two terminal Cd(II) metal ions are distorted square pyramidal.
Complex 1 exhibits extensive 2D intermolecular hydrogen bonding with respect to C–H…..Cl
along crystallographic ac-plane. The enhanced fluorescence intensities of the tri-nuclear
cadmium(II) complex 1 compared to that of di-compartmental hexadentate Schiff base ligand
(H2L1) confirmed its potentiality to be a photoactive material. Complex 1 revealed better
antibacterial activity towards some important gram positive and gram negative bacteria.
Supplementary material: Selected some bond distances, angles values and H-bonding
associated interactions. Figure S1-S3 shows complex 1 IR, UV spectral curve and complex 1 as
well as ligand excitation spectrum as supplementary information. Figure S4 as supplementary
information for complex 1 and ligand solid state fluorescence spectra.
CCDC 1495264 contains the supplementary crystallographic data (excluding structure factors) in
CIF format for the structure reported of Cd(II) tri-nuclear complex 1. The data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/ conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgement
This research work did not receive any specific grant from funding agencies in the public,
commercial or not-profit sectors. Prof. Dhrubajyoti Majumdar, Dr. Sourav Das and Dr. Jayanta
Kumar Biswas are thankful to Department of chemistry, Tamralipta Mahavidyalaya, Tamluk,

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Purba Medinipur; Institute of Infrastructure Technology Research and Management (IITRAM)
Ahmedabad 380026; Gujarat, and Department of Ecological Studies, University of Kalyani,
Kalyani-741235 , West Bengal, India for giving the necessary laboratory, library and research
facilities. Authors would like to thank TIC, Dr. S.K. Bera of the college for constant
encouragement to carry out the present research work. The authors also grateful to Vidyasagar
University, Paschimmedinipur, India, West Bengal, for providing assistance of different
instrumental facilities like IR, UV-Vis spectroscopy. Authors acknowledge the use of Perkin-
Elmer spectrofluorimeter facility at the Department of chemistry, Calcutta University, Kolkata,
India, for fluorescence study.
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