Synthesis, spectral, structural, electrochemical and

metallonuclease activities of copper(II) and

nickel(II) complexes with N/O containing ligands
SYNOPSIS SUBMITTED TO ALAGAPPA UNIVERSITY IN PARTIAL
FULFILMENT FOR THE AWARD OF THE DEGREE OF

DOCTOR OF PHILOSOPHY
IN
CHEMISTRY

By
A. Jayamani

(Reg. No: 0321)

Dr. N. Sengottuvelan, M.Sc., B.Ed., Ph.D.,

Research Supervisor

Department of Industrial Chemistry

School of Chemical Sciences
Alagappa University
(Re-accredited with A Grade by NAAC)

Karaikudi - 630 003

Tamil Nadu
India
May 2015

Synopsis
Synthesis, spectral, structural, electrochemical and metallonuclease activities of
copper(II) and nickel(II) complexes with N/O containing ligands
Artificial metallonucleases are in high demand as cellular regulators of DNA for
therapeutic or biochemical purposes [1]. Metal complexes containing site-specific
substructures and multiple reactive sites constitute a group of promising candidates for
nucleases because of their electronic and structural advantages [2]. Moreover, these
complexes generate highly cationic species that favor the electrostatic attraction to
anionic phosphate backbone of DNA. Incorporation of a DNA-targeting moiety into the
ligands can improve the selectivity of metallonucleases [3]. Chemical nucleases are redox
active coordination complexes that cleave DNA by an oxidative pathway. Direct scission
of DNA by oxidizing or hydrolytic agents is the subject matter for several current
researches in bioinorganic chemistry. Redox-active transition metal complexes in the
presence of oxidants have been extensively used for DNA cleavage reactions.
Among the transition metal based cleaving reagents, copper and nickel were
essential elements which can be estimated by the wide range of Cu/Ni proteins and
enzymes playing different roles in biological systems [4]. There is an exigency to identify
effective metal-based therapeutics, particularly those that overcome both inherent and
acquired resistance to drug therapy which show improved therapeutic properties,
stimulating the ongoing investigations of alternative molecular targeted metal-based
drugs [5]. Medicinal inorganic chemistry is a thriving interdisciplinary research area
[69] which offers exciting possibilities for the design of novel metal-based therapeutic
/diagnostic agents with unique mechanisms of action [10].

Synopsis
This Ph. D work mainly focuses on the synthesis, spectral, structural,
electrochemical and metallonuclease activities of copper(II) and nickel(II) complexes
with bidentate ligands containing N2/ O2/N2O2 donors or tetra-dentate acyclic Schiffs
base ligands containing N4 coordinating atoms. The protein binding, DNA binding,
molecular docking and antimicrobial properties of these complexes were also studied.
Chapter I
Introduction
This chapter deals with general introduction to medicinal application
of transition metal complexes, especially copper and nickel. It also
describes the types of ligands, enzymatic activity of copper and nickel
complexes, geometry and electrochemical properties of complexes,
bimolecules and their interactions with metal complexes, metallonuclease
activity of copper and nickel complexes, and antimicrobial properties. It
also critically reviews the reported copper and nickel complexes related to
their N/O chelating ligand and their properties pertaining to bidendate and
Schiffs base complexes. Literature reports show that spectral, structural,
metalonuclease properties and medicinal applicability of the complexes
are influenced by the nature of coordination geometry of the complexes
and substituent in the ligand framework. This chapter ends with list of
references of this part.

Chapter II
Aim and scope

Synopsis
The second chapter of the thesis explains the scope of the present work. The
reactivity of metal complexes towards DNA and protein BSA is important in
understanding the mechanism of binding and in the rational design of metallo-drugs.
Metal complexes containing planar heterocyclic aromatic ligands, such as 2, 2-bipyridine
and 2, 2-biimidazole or simple aromatic salicylaldehyde derivatives or bulky aromatic
naphthaldehyde derivative, have been at the forefront of these investigations owing to
their unusual electronic properties and diverse chemical reactivity. Several metal
complexes of Schiffs bases derived from salicylaldehyde and amines were also reported
and some of them have been proven to be efficient metallonuclease and as novel tumour
chemotherapeutic agents. In order to expand the knowledge in this field, we synthesized,
characterized the copper(II) and nickel(II) complexes with potential bidendate ligands,
mixed ligand and Schiffs base ligands. The spectral, electrochemical, biomolecular
interactions, metallonuclease activity and antimicrobial properties of the complexes were
studied by using various analytical tools.
Chapter III
Experimental details
The third chapter deals with the experimental details and synthetic methodology
of copper(II) and nickel(II) complexes with potential bidendate ligands which forms N4,
O4, N2O2 type of coordinations and four Schiffs base ligands with four N-donor atoms of
bappz and free phenlolic hydroxyl group of hydroxy aldehyde compounds. This chapter
also describes the various instrumental methods used during the course of study.
The

electronic

spectra

were

recorded

on

Shimadzu

UV3101PC

spectrophotometer. The IR spectra were recorded in 4000400 cm1 region using KBr

Synopsis
pellets on a Bruker EQUINOX-55 spectrometer. Fluorescence spectra were recorded on
Elico SL-174 spectrofluorometer. The circular dichroism (CD) spectra were recorded on
Jasco J-810 spectropolarimeter. Elemental analyses were carried out on an Elementar
vario MACRO cube elemental analyzer. The Electron Paramagnetic Resonance (EPR)
spectra were recorded at liquid nitrogen temperature with Varian E-112 X-band
spectrometer operating at 910 GHz (SAIF, IIT Bombay, India). The DNA cleavage
studies were visualized and photographed on BIO RAD Gel DOC XR + with image lab3.0 software. A Biologic CHI604D electrochemical analyzer was used for studying the
electrochemical behavior of complexes using a three-electrode cell in which a glassy
carbon electrode was the working electrode, a saturated Ag/AgCl electrode was the
reference electrode and a platinum wire was used as an auxiliary electrode in nitrogen
atmosphere. The concentration of complexes was 10 3 M in dimethylformamide (DMF)
and tetra(n-butyl)ammonium perchlorate (TBAP) (101 M) was used as the supporting
electrolyte. Safety note: Perchlorate salts of metal complexes are potentially explosive
and should be handled with care. The rigid molecular docking studies were performed by
using HEX 8.0 software.
Chapter IV
Results and discussions
The detailed results obtained from spectral, structural, electrochemical,
BSA/DNA binding, DNA cleavage activity and antimicrobial studies of all the
synthesized complexes are well discussed in this chapter.
Synthesis of copper(II) and nickel(II) complexes with heterocyclic bidentate ligands
containing N2 chelating donor set

Synopsis
The synthesis of Copper(II) complexes (15) of bipyridine was carried out using a
common procedure by the reaction of stoichiometric amount of chloride, perchlorate,
acetate salts of copper, bipyridine and sodium perchlorate in methanol (Scheme 1).
Cl
N

(ClO4)

Cu
N

O3ClO

CH3

(ClO4)

Cu
N

CuCl2.2H2O

ON

NO

Na(ClO4)

(ClO4)

Cu

3
Na(ClO4)
Cu(ClO4)2.6H2O
N

Cu(CH3COO)2.H2O

N
2Cu(ClO4)2.6H2O

2Cu(CH3COO)2.H2O

2NaOH

2Na(ClO4)

NaOH

CH3

Cl
O
N

H
O

O
H

Cu
O
H

(ClO4)2
N

O
H2

Cl
O

O
Cu

Cu

Cu
N

Scheme 1

The synthesis of Cu(II) and Ni(II) complexes (6 and 7, respectively) of

biimidazole were carried out using a common procedure by the reaction of stoichiometric
amounts of copper(II) perchlorate hexahydrate, nickel(II) perchlorate hexahydrate with
biimidazole in methanol (Scheme 2).
5

Synopsis
OClO3
N

HN

NH

NH

Cu

(ClO4)

HN
Cu(ClO4)2.6H2O

6
CH3OH
HN

HN

N
CH3OH

OH2
HN

Ni(ClO4)2.6H2O

NH
(ClO4)2

Ni
HN

NH

OH2

Scheme 2

Synthesis of copper(II) and nickel(II) complexes with O2 donor set ligands

The synthesis of copper(II) and nickel(II) complexes of 5-methyl salicylaldehyde,
5-bromosalicylaldehyde, 5-nitrosalicylaldehyde and 2-hydroxy-1-napthaldehyde was
carried out using a common procedure by the reaction of stoichiometric amounts of
copper(II)/ nickel(II) perchlorate salts with respective ligands in ethanol (Scheme 3).

Synopsis
X

C2H5OH

M(ClO4)2.6H2O
OH

where

M(ClO4)2.6H2O
OH

X=

O
CH3

Br

NO2

Cu

10

Ni

12

13

14

C2H5OH

M
O

Scheme 3

where M = Cu Ni
11 15

Synthesis of copper(II) complexes with mixed bidentate (N2O2 chelating) ligands

The synthesis of the dimeric copper(II) complexes were carried out using a
common procedure by reaction of stoichiometric amounts of copper(II) perchlorate salt
and respective ligands in methanol. The analytical data obtained for complexes 1623 are
consistent with the formation of dimeric copper(II) complexes (Scheme 4 and 5).

Synopsis
OClO3
O
X

N
Cu

Cu(ClO4)2.6H2O

N
OH

O
N

O
X

O3ClO

Br
N

Cu(ClO4)2.6H2O

CH3

16

NO2

18

O
Br

Cu

.2ClO4

N
OH

Cu

O
17

OClO3
N

O
N

Cu
Cu(ClO4)2.6H2O

N
OH

O
Cu
O

N
OClO3
Scheme 4

19

Synopsis
OClO3
O
X

NH

NH

Cu

OH

NH

NH

Cu(ClO4)2.6H2O

HN

Cu
HN

O
X

OClO3

CH3

20

NO2

22

Br

Br

N
OH

NH

Cu(ClO4)2.6H2O

Br

Cu
O

NH

N
O

NH

ClO4

Cu

NH

N
NH

N
NH

ClO4

21

OClO3
O

OH

NH

NH

NH

NH

Cu
O

Cu(ClO4)2.6H2O
HN

N
Cu

HN

N
OClO3

23

Scheme 5

Synthesis of acyclic Schiffs base ligands L1 - L4

The Schiffs base ligands L1 [N,N-bis(2-hydroxy-5-methylbenzyl)-1,4-bis(3iminopropyl)piperazine],

L2

[N,N-bis(2-hydroxy-5-bromobenzyl)-1,4-bis(39

Synopsis
iminopropyl) piperazine], L3 [N,N-bis(2-hydroxy-5-nitrobenzyl)-1,4-bis(3-iminopropyl)
piperazine] and L4 [N,N-bis(2-hydroxy-1-naphthyl)-1,4-bis(3-iminopropyl)piperazine]
have been synthesized as given in scheme 6.
X

X
N
N

NH2

C2H5OH

N
OH

NH2

OH

OH

NH2

NH2

CH3
Br

L1

NO2

L3

L2

C2H5OH

OH

OH

OH

L4
Scheme 6

Synthesis of mononuclear copper(II) and nickel(II) complexes with Schiffs base

ligands
The mononuclear copper(II) complexes [CuL14](ClO4)2 were synthesized from
ligand (L1-4) with copper(II) perchlorate hexahydrate in 1:1 molar ratio. (Scheme 7) and
nickel(II) complexes [Ni(bappz)](ClO4)2, [NiL1-4](ClO4)2 were synthesized from ligand
bappz, (L1-4), respectively, with nickel(II) perchlorate hexahydrate in 1:1 molar ratio.
(Scheme 8)

10

Synopsis
X
X
N
OH N

OH

N
Cu(ClO4)2.6H2O

OH
(ClO4)2

Cu
N

OH

X
X = CH3 / Br / NO2
24 25 26

N
OH N

OH

N
Cu(ClO4)2.6H2O

(ClO4)2
N

27

11

OH

Cu
N

Scheme 7

OH

Synopsis

N
H2N

NH2

Ni(ClO4)2.6H2O

NH2
Ni

(ClO4)2
NH2

28

X
N
OH N

OH

Ni(ClO4)2.6H2O

OH
(ClO4)2

Ni
N

OH

X = CH3 / Br / NO2
29 30 31

N
OH N

OH

N
Ni(ClO4)2.6H2O

OH
(ClO4)2

Ni
N

OH

32
Scheme 8

Crystal structure
The single crystals of Schiffs base ligands (L1, L2 and L4), copper(II) complexes
1-6 and 16-19, nickel(II) complexes 7, 12, 13 and 28 were obtained and the structures
were solved by X-ray crystal structure analysis.
i)

The Schiffs base ligands L1 and L2 crystallize in monoclinc P21/c space

group but ligand L4 crystallize in monoclinic P21/c space group as a dimeric

ii)

ligand.
In the crystal structure of copper(II) complexes, the geometry of Cu(II) ion in
1, 5 and 6 were distorted square pyramidal with N4O coordination; in 2 and 3

12

Synopsis
were distorted trigonal bipyramidal with N4O coordination; in 4, 16, 18 and
19 were distorted octahedral with N2O4 coordination; and in 17 was distorted
iii)

square planar geometry with N2O2 coordination.

In the crystal structure of nickel(II) complexes, the geometry of Ni(II) ion in 7
was distorted octahedral with N4O2 coordination; in 12 and 13 were square
planar with O4 coordination; and in 28 was distorted square planar with N4
coordination.

Spectral characterizations
The ESI mass spectral data of the copper(II) and nickel(II) complexes and ESR
spectra for all copper(II) complexes were obtained and showed good agreement with the
proposed structure of the complexes.
The 1H NMR and 13C NMR spectra of the ligands were analyzed to confirm the
formation of Schiffs base ligands.
The IR spectra of complexes 15 show band near 16001639 cm1 for (C=N)
group of bipyridine, at 3650 and 3625 cm 1 to the bridging OH group (4 and 5), at 3189
cm1 for N-H stretching and a band at 1315 cm 1 for N-H bending vibrations (6 and 7).
The IR spectra of complexes 811 has bands near 3095-3070 cm1 and 2895-2876 cm1for
aromatic and aldehyde CH stretching and the band at 461-568 cm1 for metal-oxygen
(MO). The IR spectra of complexes 1623 a band near 1690 cm1 for C=O (aldehyde),
1620-1650 cm1 for (C=N) group, 1530-1560 cm1 for the phenoxide bridging with the
metal ions. The IR spectrum of complexes 2432 show band in the region of 1620-1650

13

Synopsis
cm1 for (C=N), 1000-1100 cm1 and 625 cm1 for antisymmetric stretch and
antisymmetric bend of the perchlorate ions, respectively.
The electronic spectra for all complexes were obtained in DMF solution. In the
UV region of all complexes the peaks near 240290 nm due to * transition and
peaks near 300 - 450 nm due to n */ligandmetal charge transfer/metalligand charge
transfer transitions.
The copper(II) complexes of bidendate N2 donar ligands show d-d bands around
518 - 636 nm, characteristic of distorted square pyramidal/trigonal bipyramidal geometry
(1-3, 5 and 6) and 662 nm of distorted octahedral geometry (4). The copper(II) complexes
of O2 donar ligands show d-d bands around 520-560 nm characteristic of square planar
geometry (811). The mixed ligand copper(II) complexes show d-d bands around 504708 nm characteristic of distorted square planar/octahedral geometry (1619). The
Schiffs base copper(II) complexes show d-d bands around 568-594 nm which may be
distorted square planar geometry (2427). The nickel(II) complexes of biimidazole show
d-d bands at 1013, 960 and 593 nm which is characteristic of distorted octahedral
geometry (7). The nickel(II) complexes of O2 donar ligands (1215), tetradentate bappz
(28) and tetradentate acyclic Schiffs base ligands (2932) show d-d bands around 518594 nm characteristic of square planar geometry.
Hirshfeld surface calculations
The 2D full and resolved HH, NH and OH fingerprint plots of the copper(II)
and nickel(II) complexes of N2 donar ligands conveys that the complex formation of

14

Synopsis
ligands with metal ions destroy the stacking interactions in bipyridine/biimidazole,
and perchlorate and hydroxyl group cause a larger influence than other co-ligands.
Electrochemical studies
(i)

At cathodic potential
The mononuclear copper(II) complexes of bidendate N2 donar ligands exhibit one
electron quasi-reversible redox wave at cathodic potential in the region Epc = 0.63 to
0.76 V and the binuclear copper(II) complexes exhibit two one electron quasi-reversible
redox waves in the region of E1pc = 0.72 to 0.73 V & E2pc = 1.24 to 1.45 V.
The mononuclear copper(II) complexes of bidendate O2 donar ligands exhibit one
electron quasi-reversible redox wave at cathodic potential in the region at E1pc = 0.74 to
0.77 V. The mixed ligand copper(II) complexes exhibit one electron quasi-reversible
redox wave at cathodic potential in the region at E1pc = 0.74 to 0.90 V. The copper(II)
complexes of Schiffs base ligands shows one electron quasi-reversible redox wave at
cathodic potential in the region at E1pc = 0.71 to 0.85 V.
The mononuclear nickel(II) complexes exhibit one electron quasi-reversible redox
wave at cathodic potential in the region at Epc = 0.61 to 0.80 V. The nickel(II)
complexes of Schiffs base ligands and bappz shows one electron quasi-reversible redox
wave at cathodic potential in the region at Epc = 0.69 to 1.65 V.

(ii)

At anodic potential
All the mononuclear nickel(II) complexes show quasireversible one electron
transfer at anodic potential (Epa = 1.28 V for biimidazole complex, E pa = 1.08 to 1.44 V
15

Synopsis
for bidendate ligands with O2 donar set complexes and Epa = 0.88 to 1.21 V for Schiffs
base complexes).
pH-controlled molecular ion motion
The copper(II) and nickel(II) complexes of Schiffs base ligands were analysed
for molecular motions by absorption spectroscopy. Titration of the complexes with base
induces colour change of the solution and also results in the considerable change in
absorption spectrum. The increase in d-d band of the complexes indicates that the colour
and spectral changes associated to the deprotonation process. The change of the position
of copper/nickel atom from N4 compartment to N2O2 compartment was achieved by
varying the pH of the complex solution.
BSA binding studies
The BSA binding studies of the complexes copper(II) and nickel(II) complexes
were carried out using fluorescence spectroscopy and binding constant values were
determined. The association binding constant for copper(II) and nickel(II) complexes of
N2 donar ligands were in the range of 1.65 104 to 3.59 104 M-1, for copper(II) and
nickel(II) complexes of O2 donar ligands were in the range of 7.05 10 4 to 4.68 105 M1

and for Schiffs base copper(II) and nickel(II) complexes were in the range of 1.27 10 4

to 1.58 105 M-1. The binding constant values were comparitively higher for complexes
with bidentate O2 donar ligands than that of other complexes due to the difference in
planarity of the complexes.
DNA binding studies

16

Synopsis
(i)

Absorption spectroscopy
The DNA binding ability of the complexes were investigated using absorption
spectroscopy and binding constant values were determined. The Kb values for bidendate
copper(II) and nickel(II) complexes of N2 donar ligands were found to be in the range of
2.75 103 to 1.03 105 M-1 and of O2 donar ligands were in the range of 1.16 104 to
6.72 104 M-1. For mixed ligand copper(II) complexes the Kb values were in the range of
2.56 103 to 5.10 104 M-1 and for Schiffs base copper(II) and nickel(II) complexes the
Kb values were in the range of 1.63 103 to 6.20 104 M-1.

(ii)

Fluorescence spectroscopy
The DNA binding ability of the complexes were investigated using fluorescence
spectroscopy and linear SternVolmer quenching constant (Ksv) values were determined.
The Ksv values for bidendate copper(II) and nickel(II) complexes of N2 donar ligands
were found to be in the range of 3.93 104 M1 to 7.86 105 M1 and of O2 donar ligands
were in the range of 1.88 103 M1 to 1.41104 M1. For mixed ligand copper(II)
complexes the Ksv values were in the range of 2.89 103 M1 to 2.60 104 M1 and for
Schiffs base copper(II) and nickel(II) complexes the Ksv values were in the range of 2.33
103 M-1 to 1.51 105 M-1.

(iii)

Circular dichroism spectroscopy

All the complexes have shown moderate shift in the positive CD signal at 272276 nm with slight decrease/increase in intensity for both the negative ellipticity band

17

Synopsis
near 245 nm and the positive ellipticity band near 275 nm. The binding of complexes
with ctDNA was found to be in groove and electroststic binding for copper(II) and
nickel(II) bidendate N2 / O2 chelating ligands but in the case of mixed ligand copper(II)
complexes and Schiffs base copper(II)/ nickel(II) complexes the mode of binding vary
from groove binding to itercalation depending on the planarity, hetero atoms and
aromaticity of the ligand molecules.
Molecular docking studies
All the complexes were docked within the DNA duplex of sequence
d(CGCGAATTCGCG)2 dodecamer (PDB ID: 1BNA) in order to predict the chosen
binding site along with preferred orientation of the ligand and the relative binding
energies were calculated.
DNA cleavage ability of complexes
The DNA cleavage was carried out for all the complexes and their mechanistic
pathway was also studied. All the complexes show no cleavage without the addition
reactive agents (H2O2/MPA), the cleavage process was concentration dependent and all
complexes cleave efficiently at 200 M concentration. All the copper(II) complexes
cleaves pBR322 DNA in the presence of 3-mercaptopropionic acid and for the cleavage
process to occur the singlet oxygen plays a vital role for formation of involvement of
copper-oxo intermediate. All the nickel(II) complexes cleaves pBR322 DNA in the
presence of hydrogen peroxide and cleavage process preferentially proceeded by a
hydroxyl radical mechanism with OH formation. Oxidative cleavage of plasmid DNA

18

Synopsis
species may lead to the formation of hydrogen peroxide (H 2O2), and/or hydroxyl radical
(HO) species, which cause damage to the sugar and/or base.
Antimicrobial studies
All the complexes were screened for antimicrobial analysis with four pathogenic
bacteria species and two fungal species and the obtained results as zone of inhibiton have
also been compared with those of the standard drugs, amikacin and ketokonazole for
bacteria and fungi, respectively.
Chapter V
Summary and conclusions
The summary of the present work is presented in this chapter. The brief idea about
the future course of the task is also offered.
The thesis finally ends with list of references that is cited in chapter 3 and 4 of this thesis.

19

Synopsis
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Synopsis
List of papers published from this work
1. A. Jayamani, N. Sengottuvelan, S. K. Kang, Y-I. Kim, Studies on nucleic
acid/protein interaction, molecular docking and antimicrobial properties of
mononuclear nickel(II) complexes of piperazine based Schiffs base, Inorganic
Chemistry Communications, 48 (2014) 147152.
2. A. Jayamani, N. Sengottuvelan, G. Chakkaravarthi, Synthesis, structural,
electrochemical, DNA interaction, antimicrobial and molecular docking studies on
dimeric copper(II) complexes involving some potential bidentate ligands,
Polyhedron, 81 (2014) 764776.
3. A. Jayamani, V. Thamilarasan, V. Ganesan, N. Sengottuvelan, P. Manisankar, S. K.
Kang, Y-I. Kim, Synthesis of mononuclear copper(II) complexes of acyclic Schiffs
base ligands: Spectral, structural, electrochemical, antibacterial, DNA binding and
cleavage activity, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy, 122 (2014) 365374.
4. B. Saravanan, A. Jayamani, N. Sengottuvelan, G. Chakkaravarthi, V. Manivannan,
Di--hydroxido-4O:O-di--perchlorato-4O:O-bis[(2,2-bipyridine-2N,N)copper(II)], Acta Crystallographica E, 69 (2013) m600.
5. A. Jayamani, V. Thamilarasan, V. Ganesan, N. Sengottuvelan, Structural,

electrochemical, DNA binding and cleavage properties of nickel(II) complex

[Ni(H2biim)2(H2O)2]2+ of 2,2'-biimidazole, Bull. Korean Chem. Soc., 24 (2013) 1-8.

21