Research Article Synthesis, Spectroscopic Characterisation ...

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 195074 16 pageshttpdxdoiorg1011552013195074

Research ArticleSynthesis Spectroscopic Characterisation andBiopotential and DNA Cleavage Applications of Mixed Ligand4-NN-Dimethylaminopyridine Metal Complexes

C Surendra Dilip1 K Manikandan1

D Rajalaxmi (a) Subahashini2 and R Thiruneelakandan1

1 Anna University BIT Campus Tiruchirappalli Tamil Nadu 620 024 India2 Saranathan College of Engineering Panjappur Tiruchirappalli 12 Tamil Nadu 620 012 India

Correspondence should be addressed to C Surendra Dilip cs dilipyahoocoin

Received 8 May 2013 Revised 23 August 2013 Accepted 29 August 2013

Academic Editor Josefina Pons

Copyright copy 2013 C Surendra Dilip et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

The mixed ligand transition metal complexes of 4-NN-dimethylaminopyridine (DP) and chloride as primary and secondaryligands with the general formula [M(DP)

3Cl3] M = Cr(III) and Fe(III) [M1015840(DP)

4Cl2]M1015840 = Co(II) Ni(II) Cu(II) and Cd(II)

were synthesized in a microwave oven The complexes were characterized by FT-IR and UV 1HNMR 13CNMR spectra TGDTGand various physicoanalytical techniques From the magnetic moment measurements and the electronic spectral data a distortedoctahedral geometry was proposed for the complexes The complexes express similar trend of thermal behaviour such that theylose water of hydration initially with the subsequent emission of organic and inorganic fragments and leave left the metal oxidesas residue The activation thermodynamic parameters such as 119864lowast Δ119867lowast Δ119878lowast and Δ119866lowast of the metal complexes illustrate thespontaneous formation of the complexes The antimicrobial studies against various pathogenic bacterial and fungal serums insiston that the enhanced potential of the complexes over their ligand and their biopotential properties increases with concentrationThe DNA interaction of the synthesized complexes on CT-DNA was investigated by UV-Vis spectroscopy viscosity thermaldenaturation and electroanalytical experiments and their binding constants (119870

119887) were also calculated

1 Introduction

The search for soluble bioactive compounds of metals thatare suitable for nutritional supplementation to humans is along standing problem and persists to provide enough thrustfor the fundamental researchThe aromatic heterocyclic com-pounds have an extensive role in many biological systemsincluding clinical analytical and catalysis in organic synthesis[1ndash3]Metal complexes are useful for the pharmaceutical pur-poses because of their potential ability to bind DNA viamultitude interactions and cleave the duplex by virtue of theirreactivity

Understanding of the DNA-metal complexes inter-actions are driven by few applications which includetherapeutic approaches nucleic acid conformations and

nanopharmaceuticals The characterisation of DNA recogni-tion by redox and photoactive studies are substantially aidedby studying the DNA cleavage ability of the metal complexesDouble strand breaks in duplex are noteworthy to study dueto the cell lethality than single strand breaks since the doublestrand breaks are less readily renovated by the DNA repairmechanisms [4ndash8] It is remarkable that the complexes alonewere proficient in bringing about the oxidative as well as therare hydrolytic cleavage of DNA double strand The presentwork attempts to look at this aspect on the involvementof transition metal compounds on biomolecules by theantimicrobial and DNA binding and cleavage applicationswith the participation of the mixed ligand complexes of 4-NN-dimethylaminopyridine and chloride ions with somebiologically active metal ions

2 Journal of Chemistry

2 Experimental

21 Materials and Reagents All chemicals used such as 4-NN-dimethylaminopyridine (Sigma) sodium chloride(Sigma) Cr(III) Mn(II) Fe(III) Co(II) and Ni(II) chloridehexahydrates (BDH) Cd(II) and Cu(II) chloride dihydrate(Sigma) Mn(II) and Fe(III) nitrate (Sigma) disodiumsalt of ethylenediaminetetraacetic acid (EDTA) (Analar)ammonia solution (33 vv) and ammonium chloride wereof analytical reagent grade (AR) and of the highest puritySpectroscopically pure (BDH) organic solvents includingdimethyl sulphoxide methyl chloride absolute ethyl alcoholand dimethylformamine (DMF) were used Hydrochloricand nitric acids (Merck) were used for metal estimation

22 Instruments Open capillaries were used to determinemelting points and were uncorrected Elemental microanaly-ses of the separated solid chelates for C H N and S were per-formed at SAIF CUSAT Cochin The analyses were repeatedtwice to check the accuracy of the results obtainedThemolarconductance of solid complexes in DMF is measured usingSybron-Barnstead conductometer (Meter-PM6 119864 = 3406)Infrared spectra were recorded on a Perkin-Elmer FT-IR type1650 spectrophotometer in the wave number region 4000ndash200 cmminus1 using KBr pellets The solid reflectance spectrawere measured on a Shimadzu 3101 pc spectrophotometerThe molar magnetic susceptibility is measured on powderedsamples using the Faraday method The diamagnetic cor-rections were made by Pascalrsquos constant and Hg[Co(SCN)

4]

is used as a calibrant The 1H NMR spectra were recordedusing 300MHz Varian-Oxford Mercury for the deuteratedsolvent water (D

2O) and the spectra were recorded extended

from 0 to 15 ppm Cyclic voltammetric measurements werecarried out on a BAS CV 50W electrochemical analyzingsystem (accuracy plusmn10mV) Cyclic voltammograms of all thecomplexes were recorded in 1 9 water-acetonitrile solutionswith a 01M tetrabutyl ammonium perchlorate (TBAP) assupporting electrolyte and glassy carbon as the workingelectrode The thermal analyses (TG DTG and DTA) werecarried out in dynamic nitrogen atmosphere (20mLminminus1)with a heating rate of 10∘C minminus1 using Shimadzu TG-60 Hand DTA-60 H thermal analyzers

23 Synthesis ofMetal Complexes Asolution ofmetal nitrates(05mM) [Cr(III) 0133 g Mn(II) 0127 g Fe(III) 0122 gCo(II) 0119 g Ni(II) 0119 g Cu(II) 0085 g and Cd(II)0092 g] dissolved in ethanol is gradually added to a stirredethanolic solution of 4-NN-dimethylaminopyridine (DP)ligand (10mM 0122 g) in a (metal ligand) molar ratio of1 2 Further to this reaction mixture a solution of 10mMsodium chloride (10mM 0058 g) dissolved inmethanol wasadded gradually with constant stirringThe resultant mixturewas kept undisturbed and irradiated at a stable mediumpower level (600W) in amicrowave oven for about 3minutestime period

Theprecipitated solid complexeswere filtered andwashedseveral times with 50 (vv) ethanol-water to remove anytraces of unreacted starting materials Finally the complexes

were washed with diethyl ether and dried in vacuum desicca-tor over anhydrous CaCl

2 The complexes synthesised by the

microwave method have a good yield percentage (more than80 for all the complexes) over the conventional methods(which have only 50ndash70 yield) also arrived to have the sameproducts [9] The other metal ligand molar ratios (1 3 1 4etc M L) also were tried but they were not given successfulresults

24 Determination of the Metal Content A known weightof each complex is digested with concentrated nitric acidand hydrochloric acid mixture (1 3 vv) The excess acid isfumed off and the resulting solution is evaporated to drynessThe residue is then extracted with distilled water and usedfor quantitative estimation of the metal ions Cu(II) ion isestimated volumetrically by iodometric method and Zn(II)ion is estimated volumetrically by titrating against EDTAusing Eriochrome Black T as indicator Cr(III) Co(II) Ni(II)and Cd(II) ions were estimated gravimetrically as BaCrO

4

Co[Hg(SCN)4] [Ni(DMG)

2] and CdS respectively [10]

25 Biological Activity

251 Antibacterial Screening Antibacterial activity is testedagainst B subtilis S aureus E coli P aeruginosa andP vulgaris using the paper disc plate method Each ofthe compounds is dissolved in DMSO and the solutionsof the concentrations (100 and 200 120583gmL) were preparedseparately Paper discs of Whatman filter paper (number 42)of uniform diameter (2 cm) were cut and sterilized in anautoclave The paper discs soaked in the desired concentra-tion of the complex solutions were placed aseptically in thepetri dishes containing nutrient agar media (agar 20 g + beefextract 3 g + peptone 5 g) seeded with each bacterial serumsseparately The petri dishes were incubated at 37∘C andthe inhibition zones were recorded after 24 h of incubationThe antibacterial activity of a common standard antibiotictetracycline was also recorded using the same procedure asabove at the same concentrations and solvent

252 Antifungal Screening The antifungal activity of thestandard fungicide (Flucanazone) ligand and complexes wastested for their effect on the growth of microbial culturesand studied for their interaction with C Albicans A nigerand A Fumigates using Czapekrsquos agar medium having thecomposition glucose 20 g starch 20 g agar-agar 20 g anddistilled water 1000mL To this medium a requisite amountof the compounds was added The medium was then pouredinto petri plates and the spores of fungi were placed in themediumwith the help of Inoculumrsquos needleThese petri plateswere wrapped in polythene bags containing a few drops ofalcohol and were placed in an incubator at 30 plusmn 2

∘C Thecontrols were run with three replicates used in each caseThelinear growth of the fungus was recorded by measuring thediameter of the fungal colony after 96 h and the percentageinhibition was calculated by the following equation

119868 = 119889119862 minus 119889119879

119889119862times 100 (1)

Journal of Chemistry 3

Table 1 Physical and analytical data of the complexes

Complexes Colour Mol wt MP(∘C)

Yield( ) M C H N 120583eff

BMMolar cond

(Ωminus1 cm2 molminus1)

[CrCl3(DP)3] Pale brown 524 280 85 9 96(1005)

4821(4809)

585(572)

1301(1374) 372 2524

[MnCl2(DP)4] Mercedes red 604 290 80 905(910)

5550(5562)

684(662)

1810(1854) 535 2346

[FeCl3(DP)3] Reddish brown 528 290 80 1046(1060)

4802(4779)

588(552)

1320(1362) 561 2772

[CoCl2(DP)4] Pink 608 285 85 922(970)

5542(5526)

664(657)

1824(1842) 454 2193

[NiCl2(DP)4] Green 607 278 85 926(970)

5536(5526)

668(657)

1832(1845) 283 2442

[CuCl2(DP)4] olive green 612 275 85 1022(1029)

5436(5490)

686(653)

1842(1830) 182 2358

[CdCl2(DP)4] Colourless 661 280 80 922(970)

5542(5526)

679(605)

1680(1694) mdash 2525

The values of elemental analysis are found (calculated)

where 119889119862 and 119889119879 were the diameters of the fungus colony inthe control and test plates respectively wherein clear or inhi-bition zones were detected around each hole DMF (01mL)alone was used as a control under the same condition for eachorganism and by subtracting the diameter of inhibition zoneresulting with DMF from that obtained in each case bothantibacterial and antifungal activities could be calculated asa mean of the three replicates

26 DNA Binding and Cleavage Experiments The concentra-tion of CT-DNA per nucleotide [119862(119901)] was measured usingits known extinction coefficient at 260 nm (6600Mminus1 cmminus1)The absorbance for CT-DNA was measured at 260 nm(A260) and at 280 nm (A280) to check its purity Theratio A260A280 was found to be 184 indicating that CT-DNA was satisfactorily free from protein A buffer [5mMtris(hydroxymethyl) aminomethane tris pH 72 50mMNaCl] was used for the absorption viscosity and thermaldenaturation experiments

The extent of cleavage of super coiled (SC) CT-DNA(05 120583L 05 120583g) to its nicked circular (NC) form is determinedby agarose gel electrophoresis in Tris-HCl buffer (50mMpH 72) containing NaCl (50mM) In the cleavage reactionsthe 30 120583M and 20120583M complexes in 18 120583L buffer were photo-irradiated using monochromatic UV or visible light Thesamples were then incubated for 1 h at 37∘C followed byaddition to the loading buffer containing 25 bromophenolblue 025 xylene cyanol 30 glycerol (3120583L) and finallyloaded on 08 agarose gel containing 10 120583gmL ethidiumbromide Electrophoresis was carried out at 50V for 2 h inTris-borate EDTA (TBE) buffer Bands were visualized byUV light and photographed to determine the extent of DNAcleavage from the intensities of the bands using UVItec GelDocumentation System Due corrections were made for thetrace of NC DNA present in the SC DNA sample and for thelow affinity of EB binding to SC DNA in comparison to theNC form

Thermal denaturation experiments were carried out bymonitoring the absorption of CT-DNA (50 120583M) at 260 nm at

various temperatures in the presence (5ndash10120583M) and absenceof each complex The melting temperature (119879

119898 the tempera-

ture at which 50 of double-stranded DNA becomes single-stranded) and the curve width (120590119879 the temperature rangebetween which 10 and 90 of the absorption increasesoccurred) were calculated as reported

3 Results and Discussion

31 General Properties The colours and other physical prop-erties of the complexes were listed in Table 1 The complexeswere highly soluble in DMSO and DMF and were slightlysoluble in CHCl

3

32 Molar Conductance Measurements The complexes weredissolved in acetonitrile and the molar conductivity values of10minus3M solutions at 25 plusmn 2∘C were measured and the valuesexhibited (Table 1) It was concluded from the observationsthat the complexes have molar conductivity values in therange from219 to 277Ωminus1molminus1 cm2 indicating the nonionicnature of these complexes and were thus considered as non-electrolytes From the conductivity measurements it wasinferred that the chloride ionswere coordinated tometal ionsindicating that they were ligands and not simple ions [11]

33 Elemental Analyses of the Complexes Based on themetal-ligand ratio calculated by the analytical data and the natureof the electrolytes given by the conductance measurementscompositions were assigned for the prepared complexesFrom the magnetic and conductance values it was predictedthat the complexes may have the following stoichiometries[CrCl

3(DP)3] [MnCl

2(DP)4] [FeCl

3(DP)3] [CoCl

2(DP)4]

[NiCl2(DP)4] [CuCl

2(DP)4] and [CdCl

2(DP)4]

34 Infrared Spectral Analysis The ligating behaviour of4-NN-dimethylaminopyridine in the isolated complexeswas satisfactory and acceptable due to the stereostructurearrangement of the active donor sites present in the ligand


Table 2 Characteristic IR bands (cmminus1) of the ligand and its complexes

Compound []119904(C=C) +(C=N)]

[]119886(C=C) +(C=N)] 120575(C=N) Ring

breathing](OH)

(hydrated water)120575(H2O)

(hydrated water) 120592(MndashN) 120592(MndashCl)

DP 1410sh 1630sh 753s 1143s mdash[CrCl3(DP)3] 1342sh 1612sh 746sh 1170s 3439br 816m 507s 399sh[MnCl2(DP)4] 1326s 1612br 706s 1188s 3458sh 811m 472sh 397s[FeCl3(DP)3] 1309s 1559s 724sh 1199sh 3396br 826sh 498sh 388s[CoCl2(DP)4] 1308sh 1609sh 674sh 1259s 3422sh 802m 432sh 390m[NiCl2(DP)4] 1383sh 1614br 748s 1178m 3427sh 811m 495m 398sh[CuCl2(DP)4] 1390s 1616sh 759sh 1241sh 3466sh 808m 456m 372s[CdCl2(DP)4] 1381br 1612br 715s 1211sh 3445sh 823sh 470sh 380s

1000

90

80

70

60

50

40

30

20

10

00

40000 3000 2000 1500 1000 4000

339672

320328

295365

236852

234153

165425

155978 153333

141562

145068127359

130969

119951

99853

90536

82607

72439

69467

60448

52735

45591

49861

41536

(cmminus1)

T(

)

Figure 1 IR spectrum of [FeCl3(DP)3] complex

and their deviated positions from each otherrsquosThis structuralelevation of the ligand DP can express both the monodentateand bidentate attachment through the more electron densegroup of it [12] Although the ring nitrogen was more basicin comparison to the amine nitrogen it is necessary toclarify whether the coordination occurs through the ringnitrogen or amine nitrogen or both of them in a bidentatemanner When the amine nitrogen is involved in complexformation drastic changes occur in the vibrational wavenumbers of the amine group (NH stretching and bendingmodes shift to lower wave numbers and NH wagging modeshift to higher wave numbers) On the other hand when thepyridine ring nitrogen was involved in complex formationpyridine ring breathing and deformation vibrational modesincrease in value due to coupling with M-N (pyridine) bondvibrations and alterations of the force field [13]The change invibrational wave numbers of complexes from ligand supportsthe coordination of DP through the pyridine ring nitrogen

Pyridine ring vibrations of free DP at 1028 cmminus1 (ringbreathing mode) were shifted to higher frequencies in thespectra of the complexes (Table 2) The higher shift observedin ]N-C and 120575N-C bands supports the coordination of pyri-dine ring The pyridine ring breathing and deformation in

frequency band intensities were changed to higher positionsduring complex formation instructing that the pyridine ringnitrogen was coordinated These bands shift to lower wavenumbers in the complexes due to the coordination of thering nitrogen The DP shows strong bands at 1465 cmminus1 and1143 cmminus1 which were assigned to asymmetric and symmetricstretching of pyridine ring []

119904(C=C) + (C=N)] The lower

shift observed in the pyridine ring band ]119886(C=C) + (C=N)

that appeared around 1400 cmminus1 in the complex (Figure 1)supports their involvement in coordination in its neutral state[14]

Also aminor negative shift observed for ](C=C) supportstheir being sided out from complexation The water ofhydration caused a small broadband in the higher field area(3480 cmminus1) followed by another band at 890ndash810 cmminus1 Newbands appearing in the range of 541ndash526 and 304ndash297 cmminus1region of the IR spectra of the complexes (not present in thespectrum of the free ligands) were attributed to ](M-N) and](M-Cl) vibrations respectively

The complexes show ](M-Cl) band around 300 cmminus1which is similar to its assignment for terminal chloroligandsThere is no strong bands observed around 320 cmminus1 together


Table 3 Electronic spectral data and ligand field parameters of complexes

Complex ]1

]2

]3

119861 1198611015840

120573 120573 ]2]1

]3]2

LFSEkcalmolminus1

[CrCl3(DP)3] 16286 22727 31446 1168 964 0825 1750 139 138 3743[MnCl2(DP)4] 16864 26925 31625 1148 952 0829 1710 161 117 3486[FeCl3(DP)3] 15423 21428 mdash 1060 912 0860 1400 138 mdash 3678[CoCl2(DP)4] 19623 25122 28326 1104 920 0833 1670 128 112 2717[NiCl2(DP)4] 14626 17815 23679 1070 892 0833 1670 121 132 3082[CuCl2(DP)4] 12681 23616 mdash 1056 860 0814 1860 186 mdash 3336

with bands around 160 cmminus1 that have ruled out the possibil-ity of the bridging mode [15]

35 Electronic Spectral Analysis TheCr(III) complex exhibitsthree bands at 31446 cmminus1 22727 cmminus1 and 16286 cmminus1assigned to 4A

2g(F) rarr 4T

1g(P) 4A

2g(F) rarr 4T

1g(F) and

4A2g(F) rarr 4T

2g(P) transitions respectively The magnetic

moment (372 BM) was well within the range for the threeunpaired electrons The electronic spectral bands and themagnetic moment strongly support the octahedral geometryaround the Cr(III) ionThe inter electronic repulsion param-eter of the complex 1198611015840 (946 cmminus1) was found to be lower thanthe free ion value of 1168 cmminus1 suggesting the delocalisationof coordinated ligand [16]

The diffused reflectance spectrum of the Mn(II) com-plex shows three bands at 16864 cmminus1 26925 cmminus1 and31625 cmminus1 assigned to 6A

1g rarr

4T1g 6A1g rarr

4T2g(G)

and 6A1g rarr 4T

2g(D) transitions respectively The magnetic

moment value (535 BM) supports octahedral structureTheelectronic spectra of the Fe(III) complex showed strong bandsat 15423 and 21428 cmminus1 It was not possible to identify thetype of the d-d transition This was due to a strong charge-transfer (CT) band tailing from the UV-region to the visibleregion The magnetic moment of the Fe(III) complex wasobserved as 523 BM which is lower than the magneticmoment of the high spin octahedral complex Generally atentative interpretation expects the structure of Fe(III) to beoctahedral geometry with weak d-d transitions [17]

The magnetic moment of the Co(II) complex wasobserved to be 454 BMThediffused reflectance spectrumofthe complex shows three characteristic peaks at 19623 cmminus125122 cmminus1 and 28326 cmminus1 assigned to the transitions4T1g(F) rarr 4T

2g(F) 4T

1g rarr 4A

2g and 4T

1g(F) rarr 4T

1g(P)

transitions respectively indicating a high-spin octahedralgeometry The assignment of octahedral geometry to thiscomplex was further supported by its ]

2]1which lies at

128 The CFSE values of Co(II) complex were calculatedfrom transition energy ratio diagram using the ]

3]2ratio

[17] Various ligand field parameters were calculated for thecomplexes and were listed in Table 3

The Ni(II) complex is high spin with a room temperaturemagnetic moment value of 315 BM This value is in thenormal range observed for octahedral Ni(II) complexesIn addition the complex displays three bands in the solidreflectance spectrum at ]

1 14626 cmminus1 for 3A

2g rarr

3T2g

]2 17815 cmminus1 for 3A

2g rarr

3T1g (F) and ]

3 23679 cmminus1

for 3A2g rarr

3T1g (P) transitions The spectrum also shows

a band at 37173 cmminus1 that may be attributed to L-MCTcharge transfer [15]The 10Dq values 13987 cmminus1 confirm theoctahedral configuration of the complex

The spectrum of Cu(II) complex consists of broadlow intensity shoulder bands centred at 12681 cmminus1 and23616 cmminus1 The 2Eg and 2T

2g states of the octahedral Cu(II)

ion (d9) split under the influence of the tetragonal distortionthat causes three transitions 2B

1g rarr

2B2g 2B1g rarr

2Egand 2B

1g rarr

2A1g It could be concluded that all the three

transitions lie within the two broad envelopes centred at thesame range The magnetic moment of 182 BM falls withinthe range normally observed for octahedral Cu(II) complexand a moderately intense peak observed at 22469 cmminus1 wasdue to L-MCT

The diamagnetic Cd(II) complex did not show any d-dbands and its spectrumwas dominated only by a charge trans-fer band The charge transfer band at 340 nm was assignedto the transition 2Eg rarr

2T2g possibly in an octahedral

environment On the basis of the above observations anoctahedral geometry could be suggested for all the complexes[15]

36 1H NMR Spectra Studies The 1H NMR spectra of thefree DP and its complexes were recorded in DMSO-d and thepeaks were listed in Table 4The DP shows the signals for thearomatic protons at 120575 654 (H

2andH

6) and 832 (H

3andH

5)

also the amine (methyl) proton appeared at 312 Howeverthese signals were shifted downfield in the complexes by006ndash019 ppm for the aromatic protons The spectrum alsoshows a single peak at 6 ppm which was attributed to the ndashN(CH

3)2groups This signal was shifted to the upfield in the

Cd(II) complex by 022 ppm The appearance of CH3groups

in the complex were suggested that the coordination wasimpossible through the amine nitrogen This indicates thatthe DP was coordinated with the metal ions through ringnitrogen [18]

37 13C NMR Spectra Studies The 13C NMR spectrum ofthe DP shows three peaks at 15034 10756 and 15438 ppmwhich were due to (C

26) (C35) and C

4 respectively In the

complexes theC4signal thatwas adjacent to the coordination

site was shifted to up-field by 942 ppm due to deshieldingAlso the spectrum of the DP shows three signal protons at


Table 4 1H NMR chemical shift (120575 ppm) of the free ligand and itscomplexes

Compound N (CH3)2 H2 and H6 H3 and H5

DP 312 654 832[Cd(CL)2(DP)4] 334 648 813

15980 (C26) and 11830 (C

35) because of the very strong over-

lap between (C3and C

5) and (C

2and C

6) peaks However a

significant shift to the down-field by 748 ppm was observedon Cd(II) complex in amine carbon (methyl group) Thesesignals support the involvement of pyridine ring nitrogen incomplexation [19]

38 ESR Spectral Analysis The x-band ESR spectrum of thecopper complex was recorded in DMSO at 300 and 77K(Figure 2) The 119892 tensor values of copper complex are usedto derive the ground state values In octahedral complexesthe unpaired electron lies in the dx2-y2 orbitals giving 2B

1g

as the ground state From the observed values it was clearthat 119860

= 128 gt 119860

perp= 56 119892

= 242 gt 119892

perp= 213 gt

20023 and the EPR parameters of the complex coincide wellwith related systems which suggests that the complex hasoctahedral geometry (tetragonal distortion) and the systemwas axially symmetric According to Hathaway if the valueof 119866 (119866 = 119892

minus 2119892

perpminus 2) is larger than four the exchange

interaction is negligible because the local tetragonal axes aremisaligned [20] For the present complex the 119866 value is 34which suggests that the local tetragonal axis is aligned parallelor slightly misaligned and is consistent with dx2-y2 groundstate

The in plane 120590-bonding covalence parameter 1205722 wasfound to be 082 which indicates that the complex has acovalent in character The out-of-plane 120587-bonding (1205742) andin-plane 120587-bonding (120573

2) parameters were also calculated

The observed 1205732 (070) and 120574

2 (134) values indicate thatthere was a substantial interaction in the in-plane bondingwhereas the out-of-plane bonding was completely ionic Thiswas also confirmed by the values of orbital reduction factors(119870and119870

perp) In the case of pure 120590-bonding119870

sim 119870perpimplies

considerable in-plane120587-bonding while119870gt 119870perpimplies out-

of-plane 120587-bonding In the present study the observed orderfor the copper complex was 119870

(056) lt 119870

perp(1072) which

indicates the presence of significant in-plane 120587-bonding [2021]

39 Thermoanalytical Studies The proposed decompositionstages temperature ranges decomposition products and thecalculated and found weight loss percentages of the com-plexes were presented in Table 5 In most of the investigatedcomplexes the first decomposition stage was the removalof hydrated water molecules The kinetic parameters for thethermal behaviour of the complexes were calculated anddisplayed in Table 6

The gradual degradation stages representing in TGADTA andDTGcurves for [CrCl

3(DP)3] complex startedwith

decomposition at 5517∘C reflecting the thermal instability

2000 3000 4000

Figure 2 EPR spectrum of [CuCl2(DP)4] complex

referring to the hydrated water molecules expelled in thefirst step by 352 (calcd 34) weight loss The removal ofCl2molecule by 2027 (calcd 2035) in the second step

started was carried out at 1747∘CThe removal of (CH3)2NH

molecules at the third step started at 3505∘C by 2576(calcd 2586) weight losses The C

5H4N organic moiety

was expelled completely at 7794∘C as the final part by 4072(calcd 4083) weight losses The residual part represents inCrO by 1342 (calcd 1371) weights

The gradual degradation stages for [MnCl2(DP)4] com-

plex started at 5617∘C was attributed to the dehydration by252 (calcd 286) weight loss The removal of Cl

2occurred

in the subsequent decomposition started at 17142∘C by 1121(calcd 1193) weight loss The removal of major organicpart in the coordinated compound [(CH

3)2NH + C

5H4N]

happened in the continuous steps started as 35091 and58012∘C by 1433 (calcd 1511) and 4712 (calcd 4792)weight loss respectively The final residue was MnO pollutedwith carbon

The thermoanalytical profile of the [CoCl2(DP)4] com-

plex showed a mass loss in the range 526ndash908∘C thisinitial decomposition reflecting the thermal instability dueto the hydrated water molecules by a weight loss 246(calc240) This was further confirmed by the broad peak(Δ119905min = 85

∘C) on DTA which corresponds to the dehydra-tion The second step of the decomposition occurs between190 and 325∘C with a 1156 (calc 1123) mass loss thatcorresponds to the elimination of chloride ligand A broadexothermic peak between 300 and 350∘C (Δ119905max = 260

∘C) onthe DTA curve (Figure 3) was attributed to the elimination ofthe ligand The final steps reveal the removal of the organicligand by two-stage decomposition between 485ndash670∘C and720ndash990∘C [(CH

3)2NH+C

5H4N] by 1563 (calc 1543) and

4748 (calc 4846) weight lossThemass of the final residueof 2287 (calculated 2248) corresponds to CoOTheDTGcurve of the complex displays three peaks at 180 570 and872∘C These peaks were attributed to the decomposition ofthe chloride and organic ligandsThe exothermic peaks at 430and 685∘C on the DTA curve were consigned to the burningof the organic residue formed in the previous stage [22]


Table 5 Thermogravimetric data of the investigated complexes

Complex Temp range (∘C) DTG peak (∘C) Decomposedassignments

Weight loss (calcd)

Residual and weight (calcd)

[CrCl3(DP)3]

35ndash170 422 ndashH2O 349 (34)170ndash350 2658 ndashCl2 1921 (1935) Cr2O350ndash580 4555 ndashC2H6N 2456 (2474) 1322 (127)580ndash790 6801 ndashC5H4N 3952 (3981)

[MnCl2(DP)4]

30ndash160 416 ndashH2O 286 (252)160ndash330 245 ndashCl2 1112 (1153) MnO330ndash600 435 ndashC2H6N 1431 (1511) 2489 (2392)600ndash800 640 ndashC5H4N 4682 (4692)

[CoCl2(DP)4]

50ndash90 85 ndashH2O 246 (240)190ndash325 180 ndashCl2 1156 (1123) CoO485ndash670 570 ndashC2H6N 1563 (1543) 2287 (2248)710ndash990 872 ndashC5H4N 4748 (4846)

[NiCl2(DP)4]

35ndash130 355 ndashH2O 288 (265)154ndash268 2048 ndashCl2 1265 (1254) NiO269ndash488 3479 ndashC2H6N 1446 (1487) 2298 (2261)490ndash675 5757 ndashC5H4N 4703 (4733)

[CuCl2(DP)4]

30ndash130 355 ndashH2O 239 (228)112ndash234 1688 ndashCl2 1083 (1092) CuO235ndash429 3239 ndashC2H6N 1082 (1091) 3264 (3254)528ndash787 6813 ndashC5H4N 4332 (4334)

[CdCl2(DP)4]

30ndash110 65 ndashH2O 263 (242)110ndash165 130 ndashCl2 1825 (1803) CdO170ndash420 310 390 ndashC2H6N 1963 (1984) 2501 (2535)480ndash990 681 ndashC5H4N 3448 (3436)

100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14

Derivative weight (min)

Temperature (∘C)Weight ()

Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979

Heat flow endo down (mW)Weight (mg)

Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)

Figure 3 The TG DTG and DTA curves of [CoCl2(DP)4] complex

The gradual degradation stages representing in TG andDTG curves for [NiCl

2(DP)4] complex started at 40∘C for

the removal of hydrated water molecule by 288 (calcd245) and then at 1541∘C for the degradation stage afterlegal thermal stability was attributed to the removal of Cl

2 by

1165 (calcd 1145) weight lossThe removal of (CH3)2NH+

C5H4N as a whole organicmoieties in the two following steps

started at 26992 and 49015∘C by 1346 (calcd 1387) and4603 (calcd 4623) weight loss The residual part was NiOby 1725 (calcd 1811) weights In [CuCl

2(DP)4] complex


Table 6 Thermodynamic data of the thermal decomposition of metal complexes

Complex Decomp temp ∘C 119864lowast kJmolminus1 119860 sminus1 Δ119878

lowast kJmolminus1 Δ119867lowast kJmolminus1 Δ119866

lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106

minus1207 2977 4437170ndash350 5597 751 times 10 minus1327 5342 9404350ndash580 8507 249 times 10

5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106

minus1167 3099 5158160ndash330 5540 348 times 10

5minus1392 5282 9595

330ndash600 1581 344 times 10 minus4683 1543 1759600ndash800 1225 185 times 10

6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560

the TG and DTG curves show three decomposition stagesstarted at 324∘C and ended at 78704∘CThe complex revealsa relative thermal stability up to 32∘C and followed by asudden decomposition by a weight loss 209 (calcd 228)corresponding to the elimination of hydrated water The sec-ond exothermic decomposition stage started at 2355∘C cor-responding to the removal of Cl

2as a terminal organicmoiety

by 1086 (calcd 1090) weight loss The final degradationstep is overlappedwith two stageswhich are started at 5286∘Cand at 718∘C respectively which are belong to the removal of(CH3)2NHandC

5H4Norganicmoieties respectively by 1028

(calcd 1091) and 4312 (calcd 4332) weight loss and leftCuO as a residue polluted with carbon [23]

The thermoanalytical profile of the [CdCl2(DP)4] com-

plex demonstrated a weight loss initiated at 526∘C A massloss of 263 (calc 240) was observed in the range 526and 1108∘C with the endothermic peak between 60ndash65∘C(Δ119905min = 62

∘C) in the DTA which corresponds to the lossof water of crystal lattice The second step of decomposi-tion between 1125 and 1659∘C with a mass loss of 1825(calc1803) was assigned to the removal of the chlorideligandThe final step has two-stage decomposition processespertinent to the removal of the noncoordinated part of theorganic (CH

3)2NH ligand by 1963 (calc1984) weight loss

continued with the slow decomposition of remaining part ofthe coordinated ligand by 3448 (calc3436) weight lossThe endothermic peaks at 170 420∘C on the DTA curvecorrespond to the degradation of organic moiety The mass

of the final residue corresponded to CdO 125 (calc 113)The DTG curve of the complex displays that two peaks at130 and 390∘C were endorsed to the decomposition of thechloride and organic ligands The exothermic peaks at 420∘Ccan be assigned to the burning of the organic residue formedin the previous stage [24]

310 Activation Thermodynamic Parameters In order toassess the effect of the metal ion on the thermal behaviourof the complexes the order 119899 and the heat of activation 119864lowast ofthe various decomposition stages were determined from theTG and DTG and their activation parameters were tabulatedin Table 6 It could be observed from these data that theactivation energy 119864lowast increases with the degradation stepspromulgated revealing the high stability of the remaining partof the complexes suggesting a high stability of complexescharacterised by their covalence Among the complexes theactivation energy increases in the order of Cr(III) ltMn(II) ltFe(III) lt Co(II) lt Ni(II) lt Cd(II) lt Cu(II)

All the complexes have negative entropy (Δ119878 = minusve) indi-cating that the complexes were formed spontaneously byabsorbing energy A more ordered activated state of thedegradation process may be possible through the chemisorp-tions of oxygen and other decomposition products The neg-ative values of the entropies of activation were compensatedby the values of the enthalpies of activation leading to almostthe same values for the free energy of activation [24] Thepositive Δ119867lowast for all the complexes reflects the endothermic


Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)

M = Mn(II) Co(II) Ni(II) Cu(II) Cd(II)

Cl

Cl

Cl

Cl

CH3

Figure 4 Predicted structure of the metal complexes

decomposition process indicating that the formation of thecomplexes may be exothermic in nature

The positive Δ119866lowast values reveal that the free energy of thefinal residue was higher than that of the initial compoundand also the decomposition stages were nonspontaneousFrom these results it is understood that the increasing stepvalues of 119879Δ119878lowast clearly override the decreasing values of Δ119867lowasttherein reflecting that the rate of removal of the subsequentspecies will be lower than that of the preceding one [25]

311 Structure of the Complexes From the various physicalchemical discussions the structures of the complexes wereassigned as in Figure 4

312 Antibacterial Activity Themain objective of the synthe-sis of any antimicrobial compound is to inhibit the microbewithout harming other biological cells For in vitro antimi-crobial activity the metal complexes were tested against thebacteria B subtilis S aureus E coli P aeruginosa andP vulgaris The MIC values of the compounds against thegrowth of microorganisms were summarised in Table 7

20

18

16

14

12

10

8

6

4

2

0DP Cr Mn Fe Co Ni Cu Cd

B subtilisS aureusE coli

P aeruginosaP vulgaris

Figure 5 Antibacterial activity of DP and its complexes(50 120583gmLminus1)

and exhibited in Figures 5 and 6 for 100 and 200120583gmLminus1concentrations respectively

The results of the antibacterial studies lead to the follow-ing presumptions

The metal complexes were found to have superior biopo-tential in comparison to 4-NN-dimethylamino pyridineagainst the same microorganism and under identical exper-imental conditions This increase in biopotential propertyof the complexes is due to the reaction of the metal ionwith the bacterial cell Complexation considerably reducesthe polarity of the metal ions because of partial sharing of itspositive charge with the donor group (the ligand) and alsothe electron density is delocalised due to the120587 back donationThus the complexation process enhanced the lipophiliccharacter of the central metal atom and hence liposolubilityof the metal ion In this way the complexation favours thepermeation of the metal ion through the lipid layers of themicroorganismsrsquo cell membrane This permeation enhancesthe rate of uptakeaccess of themetal ion on the surface of themicroorganisms cell wall These adsorbed metal ions disturbthe respiratory process of the cells thus blocking the synthesisof proteins and in turn deactivates enzymes responsible forrespiration processes

The antibacterial activity of the complexes decreases inthe following order Cu(II) gt Cd(II) gt Ni(II) gt Co(II) gtMn(II) gt Fe(III) gt Cr(III) gt DP this suggests that thelipophilic behaviour also increases in the same order Sinceall complexes (a) have the same donating atoms which wereNCl with the same coordination number (CN for eachis 6) (b) and are neutral and there were no counter ionsand (c) except Cr(III) and Fe(III) all other have the sameoxidation number in their complexes (M2+) therefore themore effective factors for biopotential properties could be thegeometrical shape and the nature of the central atoms

The enhanced antibacterial potential of copper(II) com-plex relative to the cadmium(II) complex may be due to


Table 7 Antibacterial activity of the complexesmdashdiameter of zone of inhibition (in mm)

Compound 120583gmLminus1 Gram-positive bacteria Gram-negative bacteriaB subtilis S aureus E coli P aeruginosa P vulgaris

DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5





the fact that the Cu(II)-ligand bond formed by Cu(II) wasstronger than the Cd(II)-ligand bond which in turn mayincrease the lipophilic character of copper(II) compared tocadmium(II) Also the standard reduction potential of copperis high when compared to cadmium which may be takenas an additional reason for the higher activity of copperrelative to cadmium Also the higher antimicrobial activityof cadmium(II) complex relative to the rest of the complexesmay be due to the difference in the effective nuclear chargeof the metals This means that the cadmium(II) complexincreases the lipophilicity of the central atom by decreasingthe effective nuclear charge (polarity) [of the Cd(II)] morethan other complexes

The complexes were effectively suppressed theGram-positive strains than Gram-negative strains TheGram-positive bacteria possess a thick cell wall containingmany layers of peptidoglycan and teichoic acids in contrastthe Gram-negative bacteria have relatively thin cell wallconsisting of a few layers of peptidoglycan surrounded bya second lipid membrane containing lipopolysaccharidesand lipoproteins These differences in cell wall structure canproduce differences in antibacterial susceptibility and someantibiotics can kill only Gram-positive bacteria and theywere infective against Gram-negative pathogens [26]

It was concluded that since each comples has differentbiopotential values with the same ligand the metal seemsto play a vital role in the antibacterial activity [26] Theimportance of such work lies in the possibility that thenew compounds might be more effective as drugs againstbacteria for which a thorough investigation regarding thestructure-activity relationship toxicity and their biologicaleffects would be helpful in designing a potential antibacterialagent for therapeutic use

313 Antifungal Activity Studies A comparative study ofMICvalues of theDP and its complexes indicate that in general themetal complexes have a better fungicidal property than thefree ligand This was probably due to the improved lipophilicnature of the metal complexes rationalised mainly on thebasis of their structures possessing an additional M-N bond

Moreover coordination reduces the polarity of the metalion mainly because of the partial sharing of its positivecharge with the donor groups (the ligand) and also chargeshared (120587 back donation) within the complex system formedduring coordination This process in turn increases thelipophilic nature of the central metal atom which favoursits permeation more efficiently through the lipid layer ofthe microorganism thus destroying them more aggressively


25

20

15

10

5


C albicansA nigerA fumigates

Figure 7 Antifungal activity of DP and its complexes(200 120583gmLminus1)

(Figure 7) The toxicity of the complexes can be related to thestrength of the metal-ligand bond besides other factors suchas size of the cation receptor sites diffusion and a combinedeffect of the metal and the ligands for inactivation of thebiomolecules [27]

The antifungal activity results reveal (Table 8) that theligand and its Mn(II) and Co(II) complexes have exhibitedweak activity againstA niger andA fumigatesThe diametersof the zone of inhibition of themetal complexes were orderedas follows Cu(II) gt Ni(II) gt Cd(II) gt Cr(III) gt Fe(III) gtCo(II) gtMn(II) From the results of biological activity (bothantifungal and antibacterial) the following inferences weremade

(i) A mutual relationship exists between the germicidalactivity and the coordination environment of themetal

(ii) The ligands also supports the transport of the activemetallic moiety to the site of the action where it isreleased by hydrolysis

314 Chemical Nuclease Cleavage Study In order to assessthe chemical nuclease activities of the Co(II) Ni(II) Cd(II)and Cu(II) complexes for DNA strand scission CT-DNAwas incubated with all thementionedmetal complexes underreaction conditions separately The cleavage reaction canbe monitored by gel-electrophoresis [28] The delivery ofmetal ion to the helix locally generates oxygen or hydroxideradicals yielding an efficient DNA cleavage reaction

The [CuCl2(DP)4] complex (30 120583M in 30 120583L volume)

shows 64 cleavage of the CT-DNA duplex whereas[CdCl

2(DP)4] complex (30 120583M in 30 120583L volume) shows 33

of cleavage on 1 hour exposure at 365 nmwavelength light Atthe concentrations of 30 120583M and 40 120583M the [CuCl

2(DP)4]

complex was able to convert 64 and 68 of the initial

Table 8 Antifungal activity of the complexes and ligandmdashdiameterof zone of inhibition (mm)

Compound C albicans A niger A fumigatesDP 11 10 13[CrCl3(DP)3] 16 20 19[MnCl2(DP)4] 12 13 13[FeCl3(DP)3] 18 17 19[CoCl2(DP)4] 16 14 17[NiCl2(DP)4] 21 20 23[CuCl2(DP)4] 24 23 24[CdCl2(DP)4] 18 21 20

1 2 3 4 5 6 7 8IIIIII

Figure 8 DNA photocleavage studies of 4-NN-dimethylamino-pyridine-chloride complexes Cleavage of SC CT-DNA (02 120583g30 120583M) by four metal (II) complexes (030mM) in the presence ofreducing agent ascorbic acid (070mM) in 50mM Tris-HClNaClbuffer (pH = 72)

SC (Form I) to NC (nicked circular) (Form II) respectively(lanes 8 and 7) However the nature of reactive intermediatesinvolved in the DNA cleavage by the complexes has notbeen clear yet From Figure 8 it was seen that no obviousinhibitions were observed for the Cu(II) complex in thepresence of superoxide dismutase (SOD) (lane 6) and theresults rule out the possibility ofDNAcleavage by superoxideAddition of singlet oxygen quencher NaCl (lane 8) does notshow any appreciable effect on the chemical nuclease activityof the complex It shows that the singlet oxygen has no rolein the DNA cleavage process The addition of EtOH (lane 8)partly diminishes the nuclease activity of the Cu(II) complexthese results indicate that the involvement of hydroxyl radicalandor ldquometal-oxordquo intermediates as the reactive species inthe cleavage reaction

315 Thermal Denaturation Studies The influences of DPmetal complexes on the melting of CT-DNA were done toenumerate the information regarding metal ion binding onCT-DNA The thermal denaturation curves for CT-DNA inthe absence and in the presence of the complexes at the ratioof [DNA][complex] = 20 were given in Figure 9 and therelevant data for all the complexes investigated in this studywere summarised in Table 9Themelting studies were carriedout at the DNA complex concentration of 25 and the 119879

119898

(melting temperature) and 120590119879 values were determined bymonitoring the absorbance of DNA (within the temperaturerange at which 10 and 90 of the absorption increaseoccurred) at 260 nm as a function of temperature

In the given experimental conditions the melting tem-perature (119879

119898) of pure CT-DNA (in the absence of addition

of complexes) was found to be 70∘C With the addition of


140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu

Figure 9 Melting curves for DNA alone and in presence of 4-NN-dimethylaminopyridine complexes at 119875119863 = 20 [DNA] = 150120583M[Complex] = 75 120583M and 10mM phosphate buffer is used in theseexperiments

Table 9 Results of thermal denaturation 119879119898 studies [DNA]

[complex] = PD = 20

Complex 119879119898C∘

CT-DNA 70[CoCl2(DP)4] 74[NiCl2(DP)4] 76[CuCl2(DP)4] 86[CdCl2(DP)4] 80

complexes under similar conditions the melting tempera-ture (119879

119898) of the CT-DNA was increased by 4 6 16 and

10∘C for the [CoCl2(DP)4] [NiCl

2(DP)4] [CuCl

2(DP)4] and

[CdCl2(DP)4] complexes respectivelyThe influence ofmetal

complexes on the melting curves of the CT-DNA showsthat these complexes bind to DNA and thus increase the H-bonding between the base pairs of the double strand andincreasing the melting temperature of the nucleic acid Thelarger effect noted for the [CuCl

2(DP)4] complex suggests

that this complex binds in an intercalative mode and the restof the complexes by electrostatic groove mode

316 Absorption Spectral Features ofDNABinding OnaddingCT-DNA the complexes show a decrease inmolar absorptiv-ity of the 120587 rarr 120587

lowast absorption band indicating the insertionof the aromatic chromophores in between the base pairs ofDNA the observed trend in hypochromism reflects the trendin DNA-binding affinities of the complexes [27ndash30]

The electronic absorption spectra of copper complex inthe absence and presence ofCT-DNAwere given in Figure 10The absorption bands for the Co(II) Ni(II) Cu(II) andCd(II) complexes show hypochromism of 1595 1626

10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n

Wavelength (nm)1120583g08 120583g06 120583g

04 120583g02 120583g

Figure 10 Absorption spectra of [CuCl2(DP)4] in the presence

of CT-DNA the absorption changes upon increasing CT-DNAconcentration

3245 and 825 at 366 368 368 and 370 nm respectivelyand in each case accompanied by a small red shift by about4 4 5 and 2 nm These absorption changes suggest that theintrinsic binding constants (119870

119887) of the Co(II) Ni(II) Cu(II)

and Cd(II) complexes were 362 times 104Mminus1 383 times 104Mminus1829 times 104Mminus1 and 266 times 104Mminus1 respectively [29]

It is interesting that these complexes regardless of theirelectroneutrality nature engage in interaction with the DNAduplex and exhibit strongDNA-binding affinitiesThis stronginteraction of metal complex with the DNA may occur dueto the formation of a hydrogen bonding between the metalcomplex and the DNA base pairs [29]

The results indicate that the binding strength of complexincreases in the following order Cu gt Ni gt Co gt Cd Thissuggests an intimate association of the compounds with CT-DNA and it was also likely that these compounds bind to thehelix via an intercalative mode [30]

317 DNA Binding Electrochemical Behaviour In the cyclicvoltammogram study of the Ni(II) complex (Figure 11(a))the emf was varied from minus20V to 10 V at a scan rate of50mVsminus1 During the cathodic scan no reducible specieswas observed from 10V to minus085V and the cathodic peakobserved at minus12 V may be due to the reduction of Ni(II) intoNi(I) In the absence ofCT-DNA the Ni(II) complex exhibitsa quasireversible redox wave corresponding to Ni(II)Ni(I)with 119864pc and 119864pa values of minus0867 and minus0558V respectivelyThe ratio of anodic to cathodic peak current value was foundto be less than 1 and the formal electrode potentials 119864

12and

Δ119864119901were calculated to be 0309 and minus0712V respectivelyWith the addition of CT-DNA to Ni(II) complex the

cathodic and anodic peaks were shifted to minus0882 andminus0571V along with a shift in the formal electrode potential


minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)

Potential (V)0minus1 minus500m 500m

14m

12m

1m

(b)

Figure 11 Cyclic voltammograms of the glassy carbon electrode in solutions containing [NiCl2(DP)4] in the (a) absence and (b) presence of

CT-DNA 119881 = 01Vsminus1 (versus Ag|Ag+ electrode)

minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)

Figure 12 Cyclic voltammograms of the glassy carbon electrode in solutions containing [CuCl2(DP)4] in the (a) absence and (b) presence

of CT-DNA 119881 = 01 Vsminus1 (versus Ag|Ag+ electrode)

values to 11986412

= 0311V and Δ119864119901= minus0727V respectively

(Figure 12(b)) The ratio of 119868pa119868pc was also found to bedecreased further on addition of CT-DNA to the complexThe observed shift in the potentials and the decrease in ratioof peak currents suggest that the binding of Ni(II) complexto CT-DNA was weaker in nature Also the KNi(I)KNi(II)value of 055 suggests that a stronger binding affinity exists forthe Ni(II) state compared to the Ni(I) state in the nickel(II)complex

Cyclic voltammogram of Cu(II) complex in the absenceand presence of CT-DNA was shown in Figures 12(a) and12(b) In the absence of CT-DNA the cyclic voltammogramfeatured two anodic peaks 119864pa (0368 and minus0320V) andtwo cathodic peaks 119864pc (0113 and minus0765V) at 50mVsminus1The first reduction and oxidation potential observed at

119864pc = 0113V and 119864pa = 0368V was assigned to the redoxcouple Cu(III)Cu(II) The second reduction and oxidationpotential observed at 119864pc = minus0765V and 119864pa = minus0320Vwas attributed to the redox couple Cu(II)Cu(I) (Table 10)The ratio of 119868pa119868pc was less than unity for the above tworedox couples This also indicates that two quasireversibleone-electron transfer reduction processes were involved

In the presence of CT-DNA the cyclic voltammogramof the copper(II) complex exhibited shifts in the anodicand cathodic peak potentials in association with decrease inpeak currents thereby indicating an existence of interactionbetween the copper(II) complex and CT-DNA The dropin the voltammetric current can be attributed to the fastdiffusion of the metal complex compared to the slowlydiffusing DNA molecule The 119864

12values exhibit negative


Table 10 Electrochemical behaviour of metal complexes in the absence and presence of CT-DNA

Complex Redox couple 119864pc (V) 119864pa (V) Δ119864119901(V) 119864

12(V)

119870119877119870119874Free Bound Free Bound Free Bound Free Bound

[NiCl2(DP)4] Ni(II)Ni(I) minus0267 minus0182 minus0858 minus0571 minus0491 minus0389 0309 0311 055[CuCl2(DP)4] Cu(III)Cu(II) 0643 0478 0868 0215 0455 0263 0240 0216 025

Cu(II)Cu(I) minus0865 minus0728 minus0620 minus0450 0415 0323 minus0543 minus0516 42211986412 = 12(119864pa +119864pc) Δ119864119901 = 119864pa minus119864pc where 119864pa and 119864pc are anodic and cathodic peak potentials respectively Scan rate 50mVsminus1 119868pc and 119868pa are cathodicand anodic peak currents respectively

shifts of 0216 and minus0516V The shift in the value of theformal potential (Δ1198641015840

0) can be used to estimate the ratio

of equilibrium binding constants (119870119877119870119874) according to the

model of interaction as described by Carter et al [31] where119870119877and 119870

119874are the corresponding binding constants for the

binding of reduced and oxidized species toDNA respectivelyThe general progress can be described by a square schemeas shown in Scheme 1 similar to that proposed by Carter etal [31] The ratio of the equilibrium constants for binding ofCu(II) andCu(I) species to theDNAhas been estimated fromthe net shift in 119864

12using the following equation

119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874

119891are the formal potentials of theCu(II)Cu(I)

couple in the free and bound forms and 119870+and 119870

2+are

the corresponding binding constants for the binding of +1and +2 species to DNA respectively in each case The119870Cu(II)119870Cu(III) and 119870Cu(I)119870Cu(II) values for the copper(II)complex were calculated to be 025 and 42 respectivelysuggesting a stronger binding affinity for the Cu(II) speciescompared to the Cu(I) species The above results of metal-DNA interaction by the cyclic voltammogram studies con-firm that Cu(II) complex bound to DNA via intercalation aswell as electrostatic binding mode whereas Ni(II) complexwas bound through electrostatic binding mode

318 DNA Viscosity Measurements The values of (1205781205780)13

were plotted against [DNA][complex] concentration valuesfor the metal complexes (where 120578 and 120578

0 are the specificviscosities of DNA in the presence and absence of thecomplex resp) The viscosity of DNA decreases with andincrease in concentration of the added complexTheobserveddecreased relative viscosity may be explained by a bindingmode process which produces bends or kinks in the DNAthereby reducing its effective length and hence its viscosity

The effects of all the compounds on the viscosity of CT-DNA were shown in Figure 13 The viscosity measurementsclearly show that the Cu(II) complex can interact betweenadjacent DNA base pairs causing an extension in the DNAhelix and thus increasing the viscosity of DNA with anincreasing concentration of the solution On the basis ofall the spectroscopic studies together with the viscositymeasurements we find that the Cu(II) complex can bindto CT-DNA via an intercalative mode and the rest of thecomplex can interact with the DNA only by electrostaticmode [32]

K+ K2+

CuII (DP)4Cl2+e CuI(DP)4Cl2

CuII (DP)4Cl2-DNA CuI(DP)4Cl2-DNA

minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13

Figure 13 Viscosity titration values of CT-DNA with metal com-plexes

4 Conclusion

The mixed ligand transition metal complexes of 4-NN-dimethylaminopyridine (DP) and chloride as primary andsecondary ligands were synthesised and the complexes werecharacterised by various physicochemical and spectroscopictools The ligand 4-NN-dimethylaminopyridine has notappreciably interacted with the DNA However the syn-thesized metal(II) complexes showed a strong interactionwith the DNA Spectroscopic studies together with viscosityexperiments and electrochemical method support that thecomplexes bind to CT-DNA by partial intercalation via itspyridine ring into the base pairs of the DNA The bindingconstant shows that the DNA-binding affinity increases inthe following order Cu(II) gt Ni(II) gt Co(II) gt Cd(II) Thecomplexes are having enhanced antibacterial and antifungal


characters while compared to their parent dimethylaminopy-ridine ligand and their biopotential property increases withthe concentration Thus a few of these complexes could turnout to be a potential therapeutic material against pathogenicbiotic agents

References

[1] G Kumar R Johari and S Devi ldquoSynthesis physical charac-terization of M(III) transition metal complexes derived fromthiodihydrazide and 5-tert-butyl-2-hydroxy-3-(3-phenylpent-3-yl) benzaldehyderdquo E-Journal of Chemistry vol 9 no 4 pp2119ndash2127 2012

[2] P M Secondo J M Land R G Baughman and H L CollierldquoPolymeric octahedral and monomeric tetrahedral group 12pseudohalogeno (NCXminus X=O S Se) complexes of 4-(NN-dimethylamino)pyridinerdquo Inorganica Chimica Acta vol 309no 1-2 pp 13ndash22 2000

[3] K Kalyanasundaram andM Gratzel ldquoApplications of function-alized transition metal complexes in photonic and optoelec-tronic devicesrdquo Coordination Chemistry Reviews vol 77 no 1pp 347ndash414 1998

[4] A G Gilman L S Goodman and A Gilman The Pharmaco-logical Basis of Therapeutics Macmillan New York NY USA1980

[5] T Rosu S Pasculescu V Lazar C Chifiriuc and R CernatldquoCopper(II) complexes with ligands derived from 4-amino-23-dimethyl-1-phenyl-3-pyrazolin-5-one synthesis and biologicalactivityrdquoMolecules vol 11 no 11 pp 904ndash914 2006

[6] J R J SorensenMetal Ions in Biological Systems vol 14 MarcelDekker New York NY USA 1982

[7] M Melnik and A Sirota Challenges for Coordination Chem-istry in the New Century Slovak Technical University PressBratislava Slovakia 2001

[8] K Sharma R Singh N Fahmi and R V Singh ldquoMicrowaveassisted synthesis characterization and biological evaluation ofpalladium and platinum complexes with azomethinesrdquo Spec-trochimica Acta Part A vol 75 no 1 pp 422ndash427 2010

[9] K Deepa N T Madhu and P K Radhakrishnan ldquoCad-mium(II) complexes of 12-Di(Imino-41015840-Antipyrinyl)ethanerdquoSynthesis and Reactivity in Inorganic Metal-Organic and Nano-Metal Chemistry vol 35 no 10 pp 883ndash888 2005

[10] G H Jeffery J Bassett J Mendham and R C Denney VogelrsquoSTextbook of Quantitative Chemical AnalySiS Longman NewYork NY USA 5th edition 1998

[11] A Rai S K Sengupta and O P Pandey ldquoLanthanum(III) andpraseodymium(III) complexes with isatin thiosemicarbazonesrdquoSpectrochimica Acta vol 61 no 11-12 pp 2761ndash2765 2005

[12] K Nakamoto Infrared and Raman Spectra of Inorganic andCoordination Compounds Wiley Interscience New York NYUSA 1978

[13] C Tuc I AMorkan and SOzkar ldquoSynthesis and spectroscopiccharacterization of group 6 pentacarbonyl(4-substituted pyri-dine)metal(0) complexesrdquo Transition Metal Chemistry vol 32no 6 pp 727ndash731 2007

[14] H Icbudak H Olmez O Z Yesilel et al ldquoSyntheses character-ization and crystal structures of novel amine adducts of metalsaccharinates orotates and salicylatesrdquo Journal of MolecularStructure vol 657 no 1ndash3 pp 255ndash270 2003

[15] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1968

[16] S Cunha SM Oliveira J Ferrari et al ldquoStructural studies of 4-aminoantipyrine derivativesrdquo Journal of molecular struture vol752 no 1ndash3 pp 32ndash39

[17] R K Prakash and B Agrawal ldquoStudies on the effect of variousanions and diphenyl sulfoxide on the stereochemistry of lan-thanide(III) coordination compounds of 4[N-(21015840-hydroxy-11015840-naphthalidene)amino] antipyrinesemicarbazonerdquo TransitionMetal Chemistry vol 30 pp 696ndash705 2005

[18] RM Silverstein F XWebster andDavidKiemle SpectrometricIdentification of Organic Compounds Wiley New Delhi India2007

[19] F W Wehrli A P Marchand and S Wehrli Interpretation ofCarbon-13 NMR Spectra Wiley New York NY USA 1988

[20] B J Hathaway and D E Billing ldquoThe electronic properties andstereochemistry of mono-nuclear complexes of the copper(II)ionrdquo Coordination Chemistry Reviews vol 5 no 2 pp 143ndash2071970

[21] M Padmanabhan SMKumary XHuang and J Li ldquoSuccinatebridged dimeric Cu(II) system containing sandwiched non-coordinating succinate dianion crystal structure spectroscopicand thermal studies of [(phen)

2Cu(120583-L)Cu(phen)

2]L sdot 125H

2O

(H2L = succinic acid phen = 110-phenanthroline)rdquo Inorganica

Chimica Acta vol 358 no 13 pp 3537ndash3544 2005[22] J Zsako G Pokol Cs Novak Cs Varhelyi A Dobo and G

Liptay ldquoKinetic analyis of TG Data V Spectroscopic and ther-mal studies of some cobalt(III) chelates with ethylenediaminerdquoJournal of Thermal Analysis and Calorimetry vol 64 no 2 pp843ndash856 2001

[23] P Naumov V Jordonavska O Grupce G Jovanovski andO Grupc ldquoThermal behaviour of the n-donor adducts ofmetal saccharinates I 221015840-bipyridine saccharinato complexesof Co(II) Ni(II) Cu(II) Zn(II) and Pb(II)rdquo Journal of ThermalAnalysis and Calorimetry no 1 pp 59ndash67 2001

[24] G S Singh and T Pheko ldquoSpectroscopic characterization ofthe 1-substituted 33-diphenyl-4-(21015840-hydroxyphenyl)azetidin-2-ones Application of 13CNMR 1H-13CCOSYNMR andmassspectroscopyrdquo Spectrochimica Acta Part A vol 70 pp 595ndash6002008

[25] G Turhan-Zitouni M Sivaci F S Kilic and K Erol ldquoEuropeanjournal of medicinal chemistry synthesis of some triazolyl-antipyrine derivatives and investigation of analgesic activityrdquoEuropean Journal of Medicinal Chemistry vol 36 no 7-8 pp685ndash689 2001

[26] E Drouhet B Dupont L Improvisi M A Vivani and AM Tortorando In Vitro and in Vivo Evaluation of AntifungalAgents Elsevier Amsterdam The Netherland 1986

[27] M E Reichmann S A Rice C A Thomas and P DotyldquoA further examination of the molecular weight and size ofdesoxypentose nucleic acidrdquo Journal of the American ChemicalSociety vol 76 no 11 pp 3047ndash3053 1954

[28] M S S Babu T B Patrudu and K H Reddy ldquoDNA bindingand cleavage activity of binuclear metal complexes with benzil-120572-monoxime thiosemicarbzonerdquo E-Journal of Chemistry vol 8no 1 pp S309ndashS317 2011

[29] P S Mane S M Salunke and B S More ldquoSynthesis and struc-tural studies of transition metal complexes with bidentateschiff base derived from 3-acetyl-6-methyl-(2H)-pyran-24(3)-dionerdquo E-Journal of Chemistry vol 8 no 1 pp S245ndashS252 2011

[30] A Wolfe G H Shimer Jr and T Meehan ldquoPolycyclic aromatichydrocarbons physically intercalate into duplex regions ofdenatured DNArdquo Biochemistry vol 26 no 20 pp 6392ndash63961987


[31] M T Carter A J Bard and J Am ldquoVoltammetric studies of theinteraction of tris(110-phenanthroline)cobalt(III) with DNArdquojournal of the American Chemical Society vol 109 no 24 pp7528ndash7530 1987

[32] A Raja V Rajendiran P U Maheswari et al ldquoCopper(II)complexes of tridentate pyridylmethylethylenediamines role ofligand steric hindrance on DNA binding and cleavagerdquo Journalof Inorganic Biochemistry vol 99 no 8 pp 1717ndash1732 2005

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


2 Experimental

21 Materials and Reagents All chemicals used such as 4-NN-dimethylaminopyridine (Sigma) sodium chloride(Sigma) Cr(III) Mn(II) Fe(III) Co(II) and Ni(II) chloridehexahydrates (BDH) Cd(II) and Cu(II) chloride dihydrate(Sigma) Mn(II) and Fe(III) nitrate (Sigma) disodiumsalt of ethylenediaminetetraacetic acid (EDTA) (Analar)ammonia solution (33 vv) and ammonium chloride wereof analytical reagent grade (AR) and of the highest puritySpectroscopically pure (BDH) organic solvents includingdimethyl sulphoxide methyl chloride absolute ethyl alcoholand dimethylformamine (DMF) were used Hydrochloricand nitric acids (Merck) were used for metal estimation

22 Instruments Open capillaries were used to determinemelting points and were uncorrected Elemental microanaly-ses of the separated solid chelates for C H N and S were per-formed at SAIF CUSAT Cochin The analyses were repeatedtwice to check the accuracy of the results obtainedThemolarconductance of solid complexes in DMF is measured usingSybron-Barnstead conductometer (Meter-PM6 119864 = 3406)Infrared spectra were recorded on a Perkin-Elmer FT-IR type1650 spectrophotometer in the wave number region 4000ndash200 cmminus1 using KBr pellets The solid reflectance spectrawere measured on a Shimadzu 3101 pc spectrophotometerThe molar magnetic susceptibility is measured on powderedsamples using the Faraday method The diamagnetic cor-rections were made by Pascalrsquos constant and Hg[Co(SCN)

4]

is used as a calibrant The 1H NMR spectra were recordedusing 300MHz Varian-Oxford Mercury for the deuteratedsolvent water (D

2O) and the spectra were recorded extended

from 0 to 15 ppm Cyclic voltammetric measurements werecarried out on a BAS CV 50W electrochemical analyzingsystem (accuracy plusmn10mV) Cyclic voltammograms of all thecomplexes were recorded in 1 9 water-acetonitrile solutionswith a 01M tetrabutyl ammonium perchlorate (TBAP) assupporting electrolyte and glassy carbon as the workingelectrode The thermal analyses (TG DTG and DTA) werecarried out in dynamic nitrogen atmosphere (20mLminminus1)with a heating rate of 10∘C minminus1 using Shimadzu TG-60 Hand DTA-60 H thermal analyzers

23 Synthesis ofMetal Complexes Asolution ofmetal nitrates(05mM) [Cr(III) 0133 g Mn(II) 0127 g Fe(III) 0122 gCo(II) 0119 g Ni(II) 0119 g Cu(II) 0085 g and Cd(II)0092 g] dissolved in ethanol is gradually added to a stirredethanolic solution of 4-NN-dimethylaminopyridine (DP)ligand (10mM 0122 g) in a (metal ligand) molar ratio of1 2 Further to this reaction mixture a solution of 10mMsodium chloride (10mM 0058 g) dissolved inmethanol wasadded gradually with constant stirringThe resultant mixturewas kept undisturbed and irradiated at a stable mediumpower level (600W) in amicrowave oven for about 3minutestime period

Theprecipitated solid complexeswere filtered andwashedseveral times with 50 (vv) ethanol-water to remove anytraces of unreacted starting materials Finally the complexes

were washed with diethyl ether and dried in vacuum desicca-tor over anhydrous CaCl

2 The complexes synthesised by the

microwave method have a good yield percentage (more than80 for all the complexes) over the conventional methods(which have only 50ndash70 yield) also arrived to have the sameproducts [9] The other metal ligand molar ratios (1 3 1 4etc M L) also were tried but they were not given successfulresults

24 Determination of the Metal Content A known weightof each complex is digested with concentrated nitric acidand hydrochloric acid mixture (1 3 vv) The excess acid isfumed off and the resulting solution is evaporated to drynessThe residue is then extracted with distilled water and usedfor quantitative estimation of the metal ions Cu(II) ion isestimated volumetrically by iodometric method and Zn(II)ion is estimated volumetrically by titrating against EDTAusing Eriochrome Black T as indicator Cr(III) Co(II) Ni(II)and Cd(II) ions were estimated gravimetrically as BaCrO

4

Co[Hg(SCN)4] [Ni(DMG)

2] and CdS respectively [10]

25 Biological Activity

251 Antibacterial Screening Antibacterial activity is testedagainst B subtilis S aureus E coli P aeruginosa andP vulgaris using the paper disc plate method Each ofthe compounds is dissolved in DMSO and the solutionsof the concentrations (100 and 200 120583gmL) were preparedseparately Paper discs of Whatman filter paper (number 42)of uniform diameter (2 cm) were cut and sterilized in anautoclave The paper discs soaked in the desired concentra-tion of the complex solutions were placed aseptically in thepetri dishes containing nutrient agar media (agar 20 g + beefextract 3 g + peptone 5 g) seeded with each bacterial serumsseparately The petri dishes were incubated at 37∘C andthe inhibition zones were recorded after 24 h of incubationThe antibacterial activity of a common standard antibiotictetracycline was also recorded using the same procedure asabove at the same concentrations and solvent

252 Antifungal Screening The antifungal activity of thestandard fungicide (Flucanazone) ligand and complexes wastested for their effect on the growth of microbial culturesand studied for their interaction with C Albicans A nigerand A Fumigates using Czapekrsquos agar medium having thecomposition glucose 20 g starch 20 g agar-agar 20 g anddistilled water 1000mL To this medium a requisite amountof the compounds was added The medium was then pouredinto petri plates and the spores of fungi were placed in themediumwith the help of Inoculumrsquos needleThese petri plateswere wrapped in polythene bags containing a few drops ofalcohol and were placed in an incubator at 30 plusmn 2

∘C Thecontrols were run with three replicates used in each caseThelinear growth of the fungus was recorded by measuring thediameter of the fungal colony after 96 h and the percentageinhibition was calculated by the following equation

119868 = 119889119862 minus 119889119879

119889119862times 100 (1)





BMMolar cond



4821(4809)

585(572)

1301(1374) 372 2524


5550(5562)

684(662)

1810(1854) 535 2346


4802(4779)

588(552)

1320(1362) 561 2772

[CoCl2(DP)4] Pink 608 285 85 922(970)

5542(5526)

664(657)

1824(1842) 454 2193

[NiCl2(DP)4] Green 607 278 85 926(970)

5536(5526)

668(657)

1832(1845) 283 2442


5436(5490)

686(653)

1842(1830) 182 2358


5542(5526)

679(605)

1680(1694) mdash 2525







119898 the tempera-




3



3(DP)3] [MnCl

2(DP)4] [FeCl

3(DP)3] [CoCl

2(DP)4]

[NiCl2(DP)4] [CuCl

2(DP)4] and [CdCl

2(DP)4]





[]119886(C=C) +(C=N)] 120575(C=N) Ring

breathing](OH)




1000

90

80

70

60

50

40

30

20

10

00

40000 3000 2000 1500 1000 4000

339672

320328

295365

236852

234153

165425

155978 153333

141562

145068127359

130969

119951

99853

90536

82607

72439

69467

60448

52735

45591

49861

41536

(cmminus1)

T(

)












Complex ]1

]2

]3

119861 1198611015840

120573 120573 ]2]1

]3]2

LFSEkcalmolminus1




2g(F) rarr 4T

1g(P) 4A

2g(F) rarr 4T

1g(F) and

4A2g(F) rarr 4T




1g rarr

4T1g 6A1g rarr

4T2g(G)

and 6A1g rarr 4T




2g(F) 4T

1g rarr 4A

2g and 4T

1g(F) rarr 4T

1g(P)


2]1which lies at


3]2ratio




2g rarr

3T2g


2g rarr

3T1g (F) and ]

3 23679 cmminus1

for 3A2g rarr






1g rarr

2B2g 2B1g rarr

2Egand 2B

1g rarr







2andH

6) and 832 (H

3andH

5)






26) (C35) and C







DP 312 654 832[Cd(CL)2(DP)4] 334 648 813

15980 (C26) and 11830 (C



5) and (C

2and C

6) peaks However a



1g


= 128 gt 119860

perp= 56 119892

= 242 gt 119892

perp= 213 gt


minus 2119892





The observed 1205732 (070) and 120574






(056) lt 119870

perp(1072) which






2000 3000 4000





5H4N organic moiety




2occurred


3)2NH + C

5H4N]






3)2NH+C

5H4N] by 1563 (calc 1543) and





Weight loss (calcd)


[CrCl3(DP)3]


[MnCl2(DP)4]


[CoCl2(DP)4]


[NiCl2(DP)4]


[CuCl2(DP)4]


[CdCl2(DP)4]


100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14



Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979


Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)





2 by




2(DP)4] complex





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





BMMolar cond



4821(4809)

585(572)

1301(1374) 372 2524


5550(5562)

684(662)

1810(1854) 535 2346


4802(4779)

588(552)

1320(1362) 561 2772

[CoCl2(DP)4] Pink 608 285 85 922(970)

5542(5526)

664(657)

1824(1842) 454 2193

[NiCl2(DP)4] Green 607 278 85 926(970)

5536(5526)

668(657)

1832(1845) 283 2442


5436(5490)

686(653)

1842(1830) 182 2358


5542(5526)

679(605)

1680(1694) mdash 2525







119898 the tempera-




3



3(DP)3] [MnCl

2(DP)4] [FeCl

3(DP)3] [CoCl

2(DP)4]

[NiCl2(DP)4] [CuCl

2(DP)4] and [CdCl

2(DP)4]





[]119886(C=C) +(C=N)] 120575(C=N) Ring

breathing](OH)




1000

90

80

70

60

50

40

30

20

10

00

40000 3000 2000 1500 1000 4000

339672

320328

295365

236852

234153

165425

155978 153333

141562

145068127359

130969

119951

99853

90536

82607

72439

69467

60448

52735

45591

49861

41536

(cmminus1)

T(

)












Complex ]1

]2

]3

119861 1198611015840

120573 120573 ]2]1

]3]2

LFSEkcalmolminus1




2g(F) rarr 4T

1g(P) 4A

2g(F) rarr 4T

1g(F) and

4A2g(F) rarr 4T




1g rarr

4T1g 6A1g rarr

4T2g(G)

and 6A1g rarr 4T




2g(F) 4T

1g rarr 4A

2g and 4T

1g(F) rarr 4T

1g(P)


2]1which lies at


3]2ratio




2g rarr

3T2g


2g rarr

3T1g (F) and ]

3 23679 cmminus1

for 3A2g rarr






1g rarr

2B2g 2B1g rarr

2Egand 2B

1g rarr







2andH

6) and 832 (H

3andH

5)






26) (C35) and C







DP 312 654 832[Cd(CL)2(DP)4] 334 648 813

15980 (C26) and 11830 (C



5) and (C

2and C

6) peaks However a



1g


= 128 gt 119860

perp= 56 119892

= 242 gt 119892

perp= 213 gt


minus 2119892





The observed 1205732 (070) and 120574






(056) lt 119870

perp(1072) which






2000 3000 4000





5H4N organic moiety




2occurred


3)2NH + C

5H4N]






3)2NH+C

5H4N] by 1563 (calc 1543) and





Weight loss (calcd)


[CrCl3(DP)3]


[MnCl2(DP)4]


[CoCl2(DP)4]


[NiCl2(DP)4]


[CuCl2(DP)4]


[CdCl2(DP)4]


100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14



Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979


Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)





2 by




2(DP)4] complex





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




[]119886(C=C) +(C=N)] 120575(C=N) Ring

breathing](OH)




1000

90

80

70

60

50

40

30

20

10

00

40000 3000 2000 1500 1000 4000

339672

320328

295365

236852

234153

165425

155978 153333

141562

145068127359

130969

119951

99853

90536

82607

72439

69467

60448

52735

45591

49861

41536

(cmminus1)

T(

)












Complex ]1

]2

]3

119861 1198611015840

120573 120573 ]2]1

]3]2

LFSEkcalmolminus1




2g(F) rarr 4T

1g(P) 4A

2g(F) rarr 4T

1g(F) and

4A2g(F) rarr 4T




1g rarr

4T1g 6A1g rarr

4T2g(G)

and 6A1g rarr 4T




2g(F) 4T

1g rarr 4A

2g and 4T

1g(F) rarr 4T

1g(P)


2]1which lies at


3]2ratio




2g rarr

3T2g


2g rarr

3T1g (F) and ]

3 23679 cmminus1

for 3A2g rarr






1g rarr

2B2g 2B1g rarr

2Egand 2B

1g rarr







2andH

6) and 832 (H

3andH

5)






26) (C35) and C







DP 312 654 832[Cd(CL)2(DP)4] 334 648 813

15980 (C26) and 11830 (C



5) and (C

2and C

6) peaks However a



1g


= 128 gt 119860

perp= 56 119892

= 242 gt 119892

perp= 213 gt


minus 2119892





The observed 1205732 (070) and 120574






(056) lt 119870

perp(1072) which






2000 3000 4000





5H4N organic moiety




2occurred


3)2NH + C

5H4N]






3)2NH+C

5H4N] by 1563 (calc 1543) and





Weight loss (calcd)


[CrCl3(DP)3]


[MnCl2(DP)4]


[CoCl2(DP)4]


[NiCl2(DP)4]


[CuCl2(DP)4]


[CdCl2(DP)4]


100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14



Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979


Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)





2 by




2(DP)4] complex





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Complex ]1

]2

]3

119861 1198611015840

120573 120573 ]2]1

]3]2

LFSEkcalmolminus1




2g(F) rarr 4T

1g(P) 4A

2g(F) rarr 4T

1g(F) and

4A2g(F) rarr 4T




1g rarr

4T1g 6A1g rarr

4T2g(G)

and 6A1g rarr 4T




2g(F) 4T

1g rarr 4A

2g and 4T

1g(F) rarr 4T

1g(P)


2]1which lies at


3]2ratio




2g rarr

3T2g


2g rarr

3T1g (F) and ]

3 23679 cmminus1

for 3A2g rarr






1g rarr

2B2g 2B1g rarr

2Egand 2B

1g rarr







2andH

6) and 832 (H

3andH

5)






26) (C35) and C







DP 312 654 832[Cd(CL)2(DP)4] 334 648 813

15980 (C26) and 11830 (C



5) and (C

2and C

6) peaks However a



1g


= 128 gt 119860

perp= 56 119892

= 242 gt 119892

perp= 213 gt


minus 2119892





The observed 1205732 (070) and 120574






(056) lt 119870

perp(1072) which






2000 3000 4000





5H4N organic moiety




2occurred


3)2NH + C

5H4N]






3)2NH+C

5H4N] by 1563 (calc 1543) and





Weight loss (calcd)


[CrCl3(DP)3]


[MnCl2(DP)4]


[CoCl2(DP)4]


[NiCl2(DP)4]


[CuCl2(DP)4]


[CdCl2(DP)4]


100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14



Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979


Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)





2 by




2(DP)4] complex





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




DP 312 654 832[Cd(CL)2(DP)4] 334 648 813

15980 (C26) and 11830 (C



5) and (C

2and C

6) peaks However a



1g


= 128 gt 119860

perp= 56 119892

= 242 gt 119892

perp= 213 gt


minus 2119892





The observed 1205732 (070) and 120574






(056) lt 119870

perp(1072) which






2000 3000 4000





5H4N organic moiety




2occurred


3)2NH + C

5H4N]






3)2NH+C

5H4N] by 1563 (calc 1543) and





Weight loss (calcd)


[CrCl3(DP)3]


[MnCl2(DP)4]


[CoCl2(DP)4]


[NiCl2(DP)4]


[CuCl2(DP)4]


[CdCl2(DP)4]


100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14



Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979


Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)





2 by




2(DP)4] complex





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




Weight loss (calcd)


[CrCl3(DP)3]


[MnCl2(DP)4]


[CoCl2(DP)4]


[NiCl2(DP)4]


[CuCl2(DP)4]


[CdCl2(DP)4]


100

90

80

70

60

50

40

3071

3681

100

200

300

400

500

600

700 800

900

10006

minus2

minus4

minus6

minus8

minus10

minus12

minus14



Der

ivat

ive w

eigh

t (

min

)

Wei

ght (

)

(a)

10

9

8

7

6

5

4

3267

3681

100

200

300

400

500

600

700 800

900

10006

150

100

50

0

minus50

minus9979


Temperature (∘C)

Hea

t flow

endo

ther

mic

Wei

ght (

mg)

dow

n (m

W)

(b)





2 by




2(DP)4] complex





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





lowast kJmolminus1

[CrCl3(DP)3]

35ndash170 3077 125 times 106


5minus1460 8091 1540

580ndash790 4111 759 times 105

minus1389 3568 1263

[MnCl2(DP)4]

30ndash160 3245 295 times 106


5minus1392 5282 9595


6minus1308 1175 1956

[CoCl2(DP)4]

25ndash150 3173 471 times 105


6minus1164 7710 1085

400ndash530 1682 924 times 109


12minus724 2149 2192

[NiCl2(DP)4]

30ndash148 3821 592 times 106


6minus1093 3077 5710

300ndash510 1029 383 times 107


5minus1356 2376 9145

[CuCl2(DP)4]

30ndash130 3821 592 times 106


6minus1093 3077 5710

235ndash429 1029 383 times 107


5minus1356 2376 9145

[CdCl2(DP)4]

30ndash110 3627 565 times 106


6minus1153 3777 6220

170ndash420 988 480 times 107


5minus1466 3676 9560















Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Cl

M

M

N

N N

N

N N

N

NN

NN

NN

N

CH3

CH3

CH3 CH3

CH3

CH3

CH3

CH3

CH3

H3C

H3C

H3C

H3C

M = Fe(III) Cr(III)


Cl

Cl

Cl

Cl

CH3






20

18

16

14

12

10

8

6

4

2













DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




DP 100 08 09 05 06 06200 10 12 08 09 09

[CrCl3(DP)3]100 14 13 07 08 06200 21 21 08 06 06

[MnCl2(DP)4]100 14 13 06 07 05200 17 16 07 08 07

[FeCl3(DP)3]100 14 13 06 05 07200 16 15 08 07 08

[CoCl2(DP)4]100 15 16 10 11 11200 20 17 12 11 12

[NiCl2(DP)4]100 15 13 07 08 09200 17 17 12 12 10

[CuCl2(DP)4]100 17 18 12 13 12200 22 21 12 14 13

[CdCl2(DP)4]100 15 14 09 10 10200 21 20 12 11 10

25

20

15

10

5











25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


25

20

15

10

5













2(DP)4]




1 2 3 4 5 6 7 8IIIIII




119898






140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


140

135

130

125

120

115

110

105

100

095

20 40 60 80 100

Temperature (∘C)

Rela

tive a

bsor

banc

e

CT-DNACoNi

CdCu



[complex] = PD = 20

Complex 119879119898C∘





2(DP)4] [CuCl

2(DP)4] and








10

08

06

04

02

00

200 250 300 350 400 450 500 550 600

Abso

rptio

n


04 120583g02 120583g









12and




minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


minus1 0 1 15

Curr

ent (

A)

Potential (V)

38120583

34120583

30120583

26120583

22120583

14120583

10120583

6120583

2120583

minus2120583

minus6120583

minus10120583

minus14120583

18120583

minus500m 500m

(a)

800120583

600120583

400120583

200120583

minus200120583

minus400120583

minus600120583

minus2 minus15

0

1 15 2

Curr

ent (

A)


14m

12m

1m

(b)



minus

minus2 minus1 0 1 2

Potential (V)

minus100120583

minus200120583

minus300120583

400120583

0

600120583

500120583

400120583

300120583

200120583

100120583

Curr

ent (

A)

(a)

450120583

350120583

250120583

150120583

50120583

minus50120583

minus150120583

minus250120583

minus350120583

minus450120583

minus2 minus1 0 1 2

Potential (V)

Curr

ent (

A)

(b)



values to 11986412










12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




12(V)











119864119874

119887minus 119864119874

119891= 0059 log(

119870+

1198702+

) (2)

where119864119874119887and119864119874



2+are






K+ K2+



minus

Scheme 1

120

115

110

105

100

00 02 04 06 08 10 12 14 16 18 20 22

CrCoNiCu

ZnCd

[DNA][complex]

Mn

(120578120578

0)13


4 Conclusion




References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



References























2]L sdot 125H

2O
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of













Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Research Article Synthesis, Spectroscopic Characterisation ...

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