Research Article Synthesis and Spectroscopic and Biological...

Research ArticleSynthesis and Spectroscopic and Biological Activities of Zn(II)Porphyrin with Oxygen Donors

Gauri Devi Bajju1 Sujata Kundan1 Madhulika Bhagat2 Deepmala Gupta1

Ashu Kapahi1 and Geeta Devi1

1 Department of Chemistry University of Jammu New Campus Baba Sahib Ambedkar Road JammuJammu and Kashmir 180 006 India

2 School of Biotechnology University of Jammu New Campus Baba Sahib Ambedkar Road JammuJammu and Kashmir 180 006 India

Correspondence should be addressed to Gauri Devi Bajju gauribajjugmailcom

Received 16 October 2013 Accepted 4 December 2013 Published 16 March 2014

Academic Editor Ian Butler

Copyright copy 2014 Gauri Devi Bajju 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

Results of investigation of the physicochemical properties of zinc complexes containing substituted phenols as axial ligand havinggeneral formula [X-Zn-t(p-CH

3) PP] [where X = different phenolates as axial ligand] in impurity-free organic solvent are presented

The four-coordinated zinc porphyrin accepts one axial ligand in 1 1 molar ratio to form five-coordinated complex which is purifiedby column chromatography and characterized by physicochemical biological evaluation and TGADTA studies Absorptionspectra show two principal effects a red shift for phenols bearing substituted electron releasing groups (minusCH

3 minusNH

2) and blue

shift for phenols bearing electron withdrawing groups (minusNO2 minusCl) relative to Zn-t(p-CH

3) PP respectively 1H NMR spectra

show that the protons of the phenol ring axially attached to the central metal ion are merged with the protons of the porphyrinring Fluorescence spectra show two fluorescence peaks in the red region with emission ranging from 550 nm to 700 nm IR spectraconfirm the appearance of Zn-NPor and Zn-O vibrational frequencies respectively According to the thermal studies the complexeshave a higher thermal stability and the decomposition temperature of these complexes depends on the axial ligationThe respectivecomplexes of X-ZnII-t(p-CH

3) PP were found to possess higher antifungal activity (up to 90) and higher in vitro cytotoxicity

against human cancer cells lines

1 Introduction

The involvement of porphyrins in many biological processesand the possibility of tailoring their physical and chemi-cal properties at the molecular level make the porphyrinsand metalloporphyrins versatile synthetic base material forresearch areas due to their immense biological and fasci-nating importance in many technical applications includingbut not limited to sensors solar cells as catalysts [1ndash6]optical monomers [7 8] photocatalysts [9ndash12] photosensi-tizers in photodynamic therapy (PDT) [13] supramolecularchemistry [14 15] ionophores [16] and for the treatmentof tumors and malignant tissues [17] in combination withelectromagnetic radiation or radioactive emissions as photo-sensitizers for dye sensitized solar cells (DSSCs) [18 19]They

are also regarded as naturersquos choice catalysts and carry out aremarkable spectrum of bioenergetics reaction ranging fromphotosynthetic energy transduction to generation of ammo-nia regiospecific oxygen transfer (hydroxylation and epoxi-dation) and conversion of carbon dioxide to hydrocarbonsThe free base 5101520-meso-tetraphenylporphyrin (H

2TPP)

and themeso-substituted-tetra(ortho- and para-phenyl) por-phyrin derivatives (ndashCH

3 ndashOCH

3 ndashCl or ndashNEt

2) have been

reviewed in literature and were synthesized according to thedocumented procedure [20] Over the past decades manyexamples of axial coordination properties of metallopor-phyrins with S O P and N bases have been reported [21 22]The interaction of metalloporphyrins with donor moleculesvia axial coordination either in their ground and excitedstate can strongly influence the absorption properties and

Hindawi Publishing CorporationBioinorganic Chemistry and ApplicationsVolume 2014 Article ID 782762 13 pageshttpdxdoiorg1011552014782762

2 Bioinorganic Chemistry and Applications

the efficiency of energy or electron transfer processes [2324] This ability of metalloporphyrins to attach additionalligand (extra coordination) determines their role in enzymeand catalytic processes Mono- or bidentate complexes formdepending on the system of substituent in the porphyrinmacrocycle central ion or the nature and concentration ofthe extra ligand The reactions of extra coordination attractattention on both theoretical and experimental researches[25] Also the detailed studies on the solvation and axial lig-ation properties of ZnTPP have been reported [26 27]Theseinvestigations have shed light on how axial ligands inducechanges in the spectral absorption features and the electro-chemistry of metalloporphyrins The ability for numerouschemical modifications and the large number of differentmechanisms by which porphyrins affect microbial and viralpathogens place porphyrins into a group of compounds withan outstanding potential for discovery of novel agents pro-cedures andmaterials active against pathogenicmicroorgan-isms [28] Metalloporphyrins are the basis of new antifungalantiparasitic and anticancer drugs because modification ofthe porphyrin periphery confers qualitatively a new spectrumof activities to metalloporphyrins [29 30] Metal complexesare well known to accelerate drug action and the efficiency ofa therapeutic agent can often be enhanced upon coordinationwith a metal ion [31] Of particular interest metal ions suchas zinc which is a natural component of insulin required forthe regulation of sugarmetabolism and it is also incorporatedinto the catalytic proteins to act as a metalloenzyme thatfacilitate a multitude of chemical reactions needed for lifeZn(II) metal complexes with different ligands show overallgood potential for antibacterial antifungal antioxidant andanticancer activities [32 33] Zinc also forms low molecularweight complexes and therefore proves to bemore beneficialagainst several diseases Various biological aspects of themetal-based drugsligands entirely depend on the ease ofcleaving the bond between the metal ion and the ligand Asa consequence it is essential to understand the relationshipbetween ligand and the metal in biological systemsWith thisobjective we aimed at synthesis spectroscopic characteriza-tion and biological studies of axial zinc(II)-5101520-meso-tetra(para-methylphenyl)porphyrins with different phenolsas axial ligand

2 Experimental

21 Materials and Instruments All the chemicals were ofanalytical grade and used as received unless otherwise notedPyrrole (Fluka Switzerland) was distilled at room tempera-ture over potassium hydroxide (KOH) pellets under reducedpressure before use p-Tolualdehyde (p-methylbenzaldehyde)(Aldrich USA) propionic acid (Qualigens India) silica gel(60ndash120mesh) and silica gel (TLC grade particle size =75 120583 (Merck Germany) aluminum oxide (basic) for col-umn chromatography (Fluka Switzerland) and zinc acetate(Zn(OAc)

2sdot2H2O) (E Merck India) were used as supplied

Organic solvents were degassed by purging with prepurifiednitrogen gas and dried before use The various phenols usedwere of AR grade (Sisco Research Laboratories Pvt Ltd) andused without further purification

The optical absorption spectra of the compounds wererecorded on a Hitachi U-3400 Lambda 35 UV-Vis spec-trophotometer and Elico spectral treats UV-Vis spectrometerusing a pair of matched quartz cells of 10mm path lengthat an ambient temperature The oscillator strength (f ) of thetransitions in absorption spectra was calculated from theexpression [34]

119891 = 433 times 10

minus9120576Δ]12

(1)

where 120576 is themolar absorption coefficient in dm3molminus1 cmminus1and Δ]

12is the full width at half maximum in cmminus1 IR

spectra of complexes over the region 4000ndash400 cmminus1 wererecorded on PERKIN ELMER 580 B spectrophotometer atroom temperature using KBr discs or Nujol mulls whichconfirms the (M-N) and (M-L) vibration [35 36] The1H NMR spectra were recorded on a Bruker Avance II 400(MHz) NMR spectrometer in CDCl

3using tetramethylsilane

(TMS) as internal standard Porphyrin solutions (05mL) of10minus2 to 10minus3m in CDCl

3were used for 1HNMR studies Car-

bon hydrogen and nitrogenwere analyzedmicroanalyticallyusing CHNS analyzer Lecomodel 932 USA at a temperatureof about 1000∘C using helium as carrier gas and oxygenfor combustion The MALDI mass spectra were recorded inthe electron-impact mode on a Finnigan 3300 spectrometerusing chloroform or methanol as solvent The steady statefluorescence measurements were performed on synergy MXBiotek Multimode reader using a quartz cell of 1 cm pathlength at ambient temperature The thermogravimetric anal-yses (TGA) and differential thermal analyses (DTA) wereperformed on a Linseis STA PT-1000 in air atmosphere ata heating rate of 10∘Cmin The right angle detection wasemployed for monitoring the fluorescence

22 Biological Studies

221 Antifungal Studies The in vitro antifungal activity hasbeen done by disc diffusion method (DDM) against thepathogen and in vitro cytotoxicity against human cancer celllines In vitro antifungal activity of some of the investigatedcompounds was tested by agar plate technique against thepathogen ldquoSclerotium rolfsirdquo by the poisoned food methodusing potato dextrose agar (PDA) (glucose 20 g starch 20 gand agar-agar 20 g in 1000mL distilled water) nutrient as themedium Solution of the test compounds inDMSO (100 ppm200 ppm and 300 ppm concentrations) was prepared andmixed with the PDA The medium was then poured intosterilized Petri plates and the spores of fungi were placedon the medium with the help of inoculumrsquos needle insidelaminar flow The plates were inoculated with seven-day-oldculture of the pathogen by placing 2mm bit of the compoundunder investigation with different concentration in the centreof plates The inoculated plates were incubated at 27∘C for 5days The linear growth of fungus in control and treatmentwas recorded at different concentrations of the complexesafter 5 daysThegrowth of ldquoSclerotium rolfsirdquo over controlwascalculated as per Vincent [37]

inhibition (119868) = (119862 minus 119879)119862

times 100(2)

Bioinorganic Chemistry and Applications 3

where 119868 = percent inhibition 119862 = mean growth of fungus in(mm) in control and 119879 = mean growth of fungus in (mm) intreatment

222 In Vitro Cytotoxicity against Human Cancer Cell Lines

Cell Lines and Cell Cultures The human cancer lines wereobtained either from National Center for Cell Science PuneIndia or IIIM Jammu JampK India The human prostate(PC-3) lung (A-549) and acute lymphoblastic leukemia(THP-1) cell line was grown and maintained in RPMI-1640medium pH 74 whereas DMEMwas used for Breast (MCF-7) The media were supplemented with FCS (10) penicillin(100 unitsmL) streptomycin (100 120583gmL) and glutamine(2mM) and cells were grown in CO

2incubator (Heraeus

GmbH Germany) at 37∘C with 90 humidity and 5 CO2

Cells were treated with samples dissolved in DMSOwhile theuntreated control cultures received only the vehicle (DMSOlt02)Cytotoxicity Assay In vitro cytotoxicity against human cancercell lines was determined using sulphorhodamine B dye assay[38 39] Both test samples stock solutions were prepared inDMSO and serially diluted with growth medium to obtaindesired concentrations

23 Synthesis of Axially Ligated Zn(II) Porphyrins Complexes

231 Synthesis of 5101520-Meso-tetra(p-methylphenyl)por-phyrin [H

2t(p-CH

3)PP] The preparation of H

2-t(p-CH

3)PP

was carried out by condensation of pyrrole with p-tolualdehyde in refluxing propionic acid H

2-t(p-CH

3)PP

purified by column chromatography using chloroform aseluent (Scheme 1(a)) A second moving band was collectedafter evaporation of the solvent furnished violet colouras a title compound UV-Visible (120582nm(nm)(CHCl

3))430

516 553 592 649 1H NMR (CDCl3) minus277(s) (Imino-H)

886 (s8H120573py-H) meso-aryl protons 811 (d8HH119900) 756

(d8HH119898) 264 (s 12HHme) IR spectra (in KBr) (cmminus1)

imino ](NndashH) at 3446 aromatic ](CndashH) at 2964 ](CndashN)at 1350 ](C=C) at 1650 ](C=N) at 1589 ](CH

3) at 2855

AnalCalcd for C48H38N4() C 8604 H 571 N 86

Found C 8611 H 589 N 842

232 Synthesis of Zinc(II)5101520-Meso-tetra(p-methyl-phenyl)porphyrin [Zn119868119868-t(p-CH

3)PP] H

2-t(p-CH

3)PP (20mg

0030mmol) in chloroform (20mL) and Zn(OAc)2sdot2H2O

(20mg 0091mmol) in methanol (10mL) were refluxed for2 hrs at 60ndash70∘C till the colour of the solution changedfrom purple to red After cooling to room temperaturethe solvent was removed under reduced pressure and thesolid residue was repeatedly washed with water (3 times 60mL)to remove the excess of zinc acetate The filtered productwas dried over anhydrous sodium sulphate and purified bycolumn chromatography using (Al

2O3) as stationary phase

andCHCl3as eluent Yield of the complex [ZnII-t(p-CH

3)PP]

(18mg 80) (Scheme 1(b))UV-Vis (120582nm(nm)(CHCl

3)) 432 5642 6093 1H NMR

(CDCl3) 865 (s8H 120573py-H) 775 (d8HH

119898) 806 (d8HH

119900)

269 (s12HndashCH3) IR spectra (inKBr) (cmminus1) aromatic ](Cndash

H) appears at 2963 ](CndashN) at 1349 ](C=C) at 1658 ](C=N)at 1594 ](CH

3) at 2849 ](ZnndashN) at 482 AnalCalcd for

C48H36N4Zn1() C 7839 H 493 N 761 Found C 7846

H 499 N 772

233 Synthesis of 5101520-Meso-tetra(p-methylphenyl)por-phinatozinc(II)-phenoxide [X-Zn119868119868-t(p-CH

3)PP] It is as fol-

lows

Zn (II) -t (119901-CH3)PP + X 999447999472 X-Zn (II) -t (119901-CH

3)PP (3)

Phenol (X) (3086 times 10minus2moles) in methanol (10mL) andZn-t(p-CH

3)PP (6602 times 10minus4moles 059 g) in chloroform

(15mL) were stirred without heating for two hours Aftercompletion of reaction as indicated by TLC the reactionmix-ture was extracted with 2N NaOH solution and chloroformas an eluent The compound recovered after extraction waspassed through anhydrous Na

2SO4 The solvent was recov-

ered under reduced pressure and chromatographed throughbasic alumina using chloroform as an eluent recrystallisedwith petroleum ether and characterized by UV-Vis and 1HNMR spectra (Scheme 1(c))

3 Results and Discussion

31 Synthesis and Characterization The physical measure-ments and analytical data of all complexes with generalformula [X-ZnII-(p-CH

3)PP] (where X= different phenolates

as axial ligand) are shown in Tables 1ndash6 All the complexes arecoloured photosensitive to light and soluble in polar solventsbut water insoluble The data showing growth inhibition ofthe fungus is given in Table 7

311 1H NMR Spectroscopy The 1H NMR spectrum of themeso-tetra(p-methylphenyl)porphyrin and its Zn(II) deriva-tives containing different phenols as axial ligandwas recordedin deuterated chloroform at 298K (Table 1) The spectrumshow a singlet at minus279 ppm for inner imino protons of theH2TPP while those ofH

2-t(p-CH

3)PP resonate atminus277 ppm

The meso-aryl protons of H2TPP resonate as a singlet at

819 ppm for ortho and 759 ppm for meta and para protonsrespectively but in case of H

2-t(p-CH

3)PP the resonance

occurs at 811 ppm for ortho and 756 ppm for meta protonsthat is resonance is shifted upfield relative to H

2TPP The

methyl protons of the substituted ndashCH3group at the para-

position of the meso-aryl ring resonate as a singlet at264 ppm This effect of meso-substitution on the 120573-pyrroleprotons and meso-aryl protons has earlier been reviewed inliterature [40] Further in axially ligated zinc(II) complexesof H2-t(p-CH

3)PP a slight difference in the proton resonance

is observed depending upon the nature of the axial ligandcoordinated via zinc atom In the case of p-NO

2phO-Zn-

t(p-CH3)PP Figure 1 indicates that the 120573-pyrrole protons

resonate as a singlet at 901 ppm and the meso-aryl orthoprotons resonate as doublet at 839 ppm and 792 ppm formeso-aryl meta and para protons respectively which areslightly downfield (deshielded) compared to Zn-t(p-CH

3)PP


NHN

NHN

Propionic acid

Refluxing (12h)

5101520-meso-tetra(p-methylphenyl)porphyrin(20mg 0030mmol) (CHCl3 20mL)

(a)

CH3 + Zn(OAc)2 middot 2H2O

N

N N

NCH3

CH3

CH3

H3C

H3C

H3C Zn

Zn(II) 5101520-meso-tetra(p-methylphenyl)porphyrin(6602 times 10minus4 moles 059g) (CHCl3)

(b)

(CH3OH 10mL)

Reflux2hrs

(Phenol)(3086 times 10minus2 moles)

(CH3OH 10mL)

Chromatographedthrough

basic aluminain (CHCl3)

NN

NN

CH3

CH3

CH3

H3C Zn

X-[Zn(II)-t(p-CH3)PP]


(pure)(c)

Recrystallised withpetroleum ether

-Oph

120572-Naphthol

CHO

+

NH

CH3

44CH3 + X

CH3

CH3

CH3

CH3

X

N

N N

NZn

X

Refluxing on magneticstirrer without heating

2hrs

(crude)

Extr

actio

n

chlo

rofo

rm as

an el

uent

Passed throughanhydrous Na2SO4

(20mg 0091mmol) (60ndash70∘C)

2NN

AOH

and

X (axial ligands) = o- m- and p-NH2Oph

o- m- and p-OCH3Oph

o- m- and p-NO2Oph

o- m- and p-ClOph

24-Dichlorophenol

Scheme 1 General synthetic route for the synthesis of zinc(II)-5101520-meso-tetra(para-methylphenyl)porphyrin containing differentphenols as axial ligand

as well as forH2-t(p-CH

3)PPThemethyl protons of themeso-

aryl rings resonate at 265 ppm But in case of p-OCH3phO-

Zn-t(p-CH3)PP (Figure 2) the 120573-pyrrole protons resonate as

a singlet at 893 ppmand themeso-aryl ortho protons resonateas doublet at 822 ppm and 766 ppm for meta and pararespectively which are slightly upfield (shielded) comparedto Zn-t(p-CH

3)PP as well as for H

2-t(p-CH

3)PP The methyl

protons of the meso-aryl rings resonate at 231 ppm and themethoxy protons of para-methoxy phenolate resonate assinglet at 336 ppm The 1H NMR data of various axiallyligated Zn(II) complexes of H

2t(p-CH

3)PP revealed that

phenols with electron-withdrawing groups like ndashNO2 ndashCl

caused slight downfield shift (deshielding) and those withelectron releasing group like ndashCH

3 ndashOCH

3 and ndashNH

2

caused upfield shift (shielding) of protons with respect to Zn-t(p-CH

3)PP and H

2t(p-CH

3)PP complexes

312 Absorption Spectroscopy The electronic spectra of atypical porphyrin contain one intense band in the near-ultraviolet region of the spectrum around 400 nm (the soretband or B-band) depending on whether the porphyrin is 120573-or meso-substituted with 120576 gt 2 times 105 followed by four low-intensity absorption bands at 514 nm 550 nm 591 nm and647 nm (the Q-band) that is Qy(10) Qy(00) Qx(10) andQx(00) respectively The B- and Q-bands both arise from120587 rarr 120587

lowast transition and can be explained by four frontierorbitals (HOMO and LUMO orbitals) (the Gouterman fourorbital model) Ongoing from porphyrin to metallopor-phyrin the ring symmetry of the planarmacrocycle fragmentincreases to D

4h from D2h due to which the spectrum

is simplified The optical absorption data Zn(II)-5101520-meso-tetra(p-methylphenyl)porphyrin containing differentphenols as axial ligand in chloroform is listed in (Table 2)


Table 1 1H NMR dataa of free base H2-t(p-CH3)PP and axially ligated X-Zn-t(p-CH3)PP (X = different phenols as axial ligand) in CDCl3 at298K

Porphyrins 120573-Pyrroleprotons

Iminoprotons Meso-aryl protons Other protons

H2t(p-CH3)PP[(C48H38N4)]

886 (s) minus277 (s) 811(d 8H H119900)

756(d 8H H119898) 264(s 12H Hme)

Zn-t(p-CH3)PP[(C48H36N4Zn1)]

865 (s) mdash 806(d 8H H119900)

775(m 8H H119898) 269(s 12H Hme)

phO-Zn-t(p-CH3)PP[(C6H5O)Zn(C48H36N4)]

899 (s) mdash 841(d 10H H119900)

776(d 11H H119898119901

) 271(s 12H Hme)

p-Cl-Zn-t(p-CH3)PP[(C6H4ClO)Zn(C48H36N4)]

92 (s) mdash 829(d 10H H119900)

792(d 10H H119898) 29(s 12H Hme)

p-OCH3phO-Zn-t(p-CH3)PP[(C7H7O2)Zn(C48H36N4)]

893 (s) mdash 822(d 10H H119900)

766(d 10H H119898)

231(s 12H Hme)336(s 3H Home)

p-NH2phO-Zn-t(p-CH3)PP[(C6H6NO)Zn(C48H36N4)]

890 (s) mdash 826(d 10H H119900)

769(m 10H H119898)

236(s 12H Hme)509(s 2H HNH2

)24-Cl2phO-Zn-t(p-CH3)PP[(C6H3Cl2O)Zn(C48H36N4)]

94 (s) mdash 833(d 10H H119900)

796(d 10H H119898) 33(s 12H Hme)

p-NO2phO-Zn-t(p-CH3)PP[(C6H4NO3)Zn(C48H36N4)]

901 (s) mdash 839(d 10H H119900)

792(d 10H H119898) 265(s 12H Hme)

a120575 in ppm the nature of splitting pattern(s) (s = singlet d = doublet t = triplet and m = multiplet) number of proton(s) and their location in the porphyrinsrespectively are given in parenthesis o = ortho p = param = meta

(ppm)9 8 7 6 5 4 3 2 1 0

Methyl-H

lowast lowast

lowast

lowast

Phmeso

Phmeso

839(d10HHo)

792(d10HHm)

Pyrrole-H901(s8H)

Inte

rnal

1000

1129

1256

0910

1681

13622

1257

Figure 1 1H NMR spectra of p-NO2phO-Zn-t-(p-CH

3)PP in

CDCl3 at 298K Starred peaks are solvents impurities

The optical absorption spectra of X-Zn-t(p-CH3)PP (X =

different phenols as axial ligand) in chloroform revealedthat phenols containing electron withdrawing groups showblue shift (hypsochromic shift) while those having electronreleasing groups show red shift (bathochromic shift) that istowards longer wavelength When absorption spectra of axi-ally ligated Zn-t(p-CH

3)PP is recorded in different solvents

(Table 3) it was observed that the spectra of p-NH2phO-

Zn-t(p-CH3)PP (Figure 3) shows only a marginal change in

120582max absorption coefficient (120576) and oscillator strength (119891)values The data also reveal that a change in polarity ofthe solvents does not significantly alter the position of thetransition but there is a significant increase in ldquoFwhmrdquo (]

12)

and ldquo119891rdquo values of transition by increasing the polarity of thesolvent In polar solvents such as methanol ethanol CH

2Cl2

(ppm)9 8 7 6 5 4 3 2 1 0

lowast lowast

lowast

Inte

rnal

1000

1129

1256

0910

1681

13622

1257

Methyl-H

Phmeso

Phmeso

822(d10HHo)766(d10HHm)

Pyrrole-H893(s8H)

-OCH3-H

Figure 2 1H NMR spectra of p-OCH3phO-Zn-t-(p-CH

3)PP in

CDCl3at 298K Starred peaks are solvents impurities

CHCl3 the 120587 rarr 120587lowast band undergoes red shift and was

stable but in nonpolar solvents such as benzene toluene andCCl4 however the complexes usually displayed a spectral

drift for a period of time It is observed that for all theaxially ligated Zn(II) derivatives B- and Q-bands exhibita red shift on increasing the polarity of the solvents inthe order MtOH gt CHCl

3gt CH

2Cl2gt CCl

4 As in the

case of p-NH2phO-Zn-t(p-CH

3)PP (Figure 3) 120582max values in

MtOHwere observed at 4359 nm 589 nm and 604 nmwhilein CHCl

3 CH2Cl2 and CCl

4were observed at 4339 nm

5709 nm and 6046 nm 4328 nm 5684 nm and 601 nmand 430 nm 5601 nm and 586 nm respectively Howeverboth B(00) and Q(10) exhibit only a small change in the fvalue which depend on the nature of the solvent The f valuefor Q(10) in MtOH CHCl

3 CH2Cl2 and CCl

4was observed


Table 2 Optical absorption data of X-Zn-t(p-CH3)PP (X = different phenols as axial ligand) in CHCl3 showing 120582max together with log 120576 and]12

Porphyrins B-bands 120582max (log 120576) ]12(nm) (dm3molminus1cmminus1) (cmminus1)

Q-bands 120582max (log 120576) ]12(nm) (dm3molminus1cmminus1) (cmminus1)


430 (5986) 9894 516 553 592 649


432 (5824) (9953) 5642 (4218) 78936093 (4160)


4302 (5771) (9979) 5638 (4312) 78515986 (4289)

120572-Naphthol-Zn-t(p-CH3)PP[(C10H7O)Zn(C48H36N4)]

4314 (5798) (1008) 5640 (4418) 82946004 (4389)

o-OCH3phO-Zn-t(p-CH3)PP[(C7H7O2)Zn(C48H36N4)]

432 (5833) (9808) 5694 (4484) 82626096 (4338)

m-OCH3ph-Zn-t(p-CH3)PP[(C7H7O2)Zn(C48H36N4)]

4319 (5845) (9789) 5702 (4521) 78936083 (4432)


4324 (5808) (9841) 567 (4448) 8224604 (4392)

o-NH2phO-Zn-t(p-CH3)PP[(C6H6NO)Zn(C48H36N4)]

4334 (5806) (998) 5724 (4527) 79626063 (4486)

m-NH2phO-Zn-t(p-CH3)PP[(C6H6NO)Zn(C48H36N4)]

4332 (5696) (9924) 5704 (4456) 69866051 (4412)


4339 (5859) (9866) 5709 (4432) 69946046 (4398)

o-CH3phO-Zn-t(p-CH3)PP[(C7H7O)Zn(C48H36N4)]

431 (5964) (9871) 565 (4643) 7621596 (4431)

m-CH3phO-Zn-t(p-CH3)PP[(C7H7O)Zn(C48H36N4)]

4318 (5839) (9864) 564 (4682) 7609588 (4432)

p-CH3phO-Zn-t(p-CH3)PP[(C7H7O)Zn(C48H36N4)]

4316 (5969) (9869) 564 (4861) 7606587 (4743)

o-NO2phO-Zn-t(p-CH3)PP[(C6H4NO3)Zn(C48H36N4)]

428 (5942) (9989) 546 (4549) 8542581 (4431)

m-NO2phO-Zn-t(p-CH3)PP[(C6H4NO3)Zn(C48H36N4)]

427 (5841) (9952) 546 (4643) 8469580 (4428)


427 (5872) (9956) 546 (4516) 8428578 (4314)

o-ClphO-Zn-t(p-CH3)PP[(C6H4ClO)Zn(C48H36N4)]

426 (5646) (10144) 547 (4569) 8723575 (4321)

m-ClphO-Zn-t(p-CH3)PP[(C6H4ClO)Zn(C48H36N4)]

425 (5781) (9925) 548 (4439) 7819579 (4532)

p-ClphO-Zn-t(p-CH3)PP[(C6H4ClO)Zn(C48H36N4)]

425 (5841) (9986) 548 (4598) 7852579 (4514)

at 0206755 0253434 01878264 and 01331380 respectivelyIt was found that with the increase in polarity of the solventsthe axially ligated Zn(II) metalloporphyrin with differentphenols as axial ligand shows the progressive broadening ofthe B- and Q-bands indicating that the magnitude of changeof the ldquof rdquo value depends on the nature of the solvent and alsoreveals the relative strength of 120587 rarr 120587lowast interactions

313 Infrared Spectroscopy The vibrational spectroscopy (IRspectroscopy) can provide ample information about thestructure of porphyrin and metalloporphyrinThe IR spectraof free-base porphyrin H

2-t(p-CH

3)PP and its axially ligated

zinc(II) metal derivatives containing different phenols as

axial ligand exhibit strong absorption band at 2855 cmminus1(2850ndash3000 cmminus1) due to ndashCH

3group at meso-phenyl posi-

tion The metallation of porphyrin and axial ligation withdifferent phenols were further supported by the emergence oftwo new bands at 500ndash400 cmminus1 and 650ndash350 cmminus1 assignedto zinc-nitrogen (Zn-NPor) [41] and zinc-oxygen (ZnndashO)vibrational modes respectively In order to determine themode of bonding of different phenols as ligand with zincthe IR spectra of ligands were compared with those of cor-responding complexes (Table 4) The IR spectra of free-baseporphyrin (H

2-t(p-CH

3)PP) and its axially ligated zinc(II)

metal derivatives containing different phenols as axial lig-and showing different band frequencies agree well with


Table 3 Optical absorption data of X-Zn-t(p-CH3)PP (X = different phenols as axial ligand) recorded in different solvents with calculatedldquof rdquo values

Porphyrins SolventB-band 120582max (log 120576) ]12(nm) (dm3molminus1cmminus1)

(cmminus1)

Q-bands 120582max (log 120576) ]12 (nm)(dm3molminus1cmminus1) (cmminus1)

Oscillator strength(f = 433 times 10minus9120576Δ]

12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536

m-NO2phOZn-t(p-CH3)PP[(C6H4NO3)Zn(C48H36N4)]

MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695

the literature [42] For example in the IR spectra of24-Cl

2phO-Zn-t(p-CH

3)PP aromatic ](CndashH) vibrates at

2963 cmminus1 ](CndashN) at 1349 cmminus1 ](C=C) at 1659 cmminus1](C=N) at 1594 cmminus1 ](CH

3) at 2846 cmminus1 and ](Zn-NPor) at

476 cmminus1 and ](ZnndashO) of phenolate appears at 517 cmminus1 andin p-OCH

3phO-Zn-t(p-CH

3)PP aromatic ](CndashH) vibrates

at 2964 cmminus1 ](CndashN) at 1350 cmminus1 ](C=C) at 1654 cmminus1](C=N) at 1590 cmminus1 ](CH

3) at 2859 cmminus1 ](Zn-NPor) at

481 cmminus1 ](ZnndashO) of phenolate at 526 cmminus1 and themethoxy(ndashOCH

3) group at the para-position of the phenolate vibrates

at 2850 cmminus1 for (]1)(CndashH) 1020 cmminus1 for (]

2)(CndashOndashC)sym

and 1261 cmminus1 for (]3)(CndashOndashC)asym respectively The for-

mations of the axially ligated Zn(II) metal complexes werealso confirmed by their mass spectral data given in theexperimental section

314 Mass Spectroscopy and Elemental Analysis The massspectra of several porphyrins and their metalloderivativeshave been obtained by mass spectroscopy technique Themolecular mass [43] spectra of porphyrins and their deriva-tives are best recorded at the lowest possible temperature(usually approx 200ndash250∘C) The intensity of molecular ionin the mass spectra of porphyrin has also been used inthe study of deuteration (as a general example of electrophilic

substitution) of porphyrins metalloporphyrins and somereduced derivatives Table 5 summarizes themass spectra andelemental analysis data of axially ligated Zn(II) derivates

315 Fluorescence Spectroscopy An important and uniquefeature of porphyrins and their metal derivatives is theiremission spectra The fluorescence emission data [44 45]of the porphyrins provide important information on thesinglet excited state properties The optical properties areaffected by the presence of substituents at 120573-pyrrole and atmeso-aryl positions of the tetraphenylporphyrinsThe axiallyligated metalloporphyrins exhibited two fluorescence bandsone from S

2rarr S0(B-band) and the other from S

1rarr

S0(Q-band) Internal conversion from S

2to S1is rapid so

that there is hardly any fluorescence absorption detected fromS2rarr S1The S

2rarr S0(soret band) fluorescence is about two

orders of magnitude weaker than S1rarr S0of Q-band emis-

sion However the emission bands of axially ligated Zn(II)porphyrins are red shifted compared to Zn-t(p-CH

3)PP The

intensities of low energy Q(10) are more intense than highenergy Q(00) band in contrast to that observed for thefree-base porphyrins On comparing the fluorescence behav-ior of Zn-t(p-CH

3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in

dry methanol at room temperature using excitation atsim550 nm (Table 6) (Figure 4) it is clear from the figure that


Table 4 Main vibrational frequencies corresponding to the various groups in X-Zn-t(p-CH3)PP (X = different phenols as axial ligand)

∙∙

∙∙

N

O

NN

N

Zn

Porphyrins ](NndashH)(cmminus1)

](CndashH)(cmminus1)

](CndashN)(cmminus1)

](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)

](ZnndashNpor)(cmminus1)

](ZnndashO)(cmminus1) Other assignments


3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850

]2(CndashOndashC)sym = 1020

]3(CndashOndashC)asym = 1261


mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527

24-Cl2phO-Zn-t(p-CH3)PP[(C6H3Cl2O)Zn(C48H36N4)]

mdash 2963 1349 1659 1594 2846 476 517

p-CH3-phO-Zn-t(p-CH3)PP[(C7H7O)Zn(C48H36N4)]

mdash 2951 1346 1642 1580 2862 468 519

Table 5 Mass data (mz ratio) and elemental analytical data of X-Zn-t(p-CH3)PP (X = different phenols as axial ligand) along with theircalculated values

Porphyrins Molecular formula mz ratiocalculated (found)

Percentage calculated (found)C H N


C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)

24Cl2phO-Zn-t(p-CH3)PP[(C6H3Cl2O)Zn(C48H36N4)]

C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)

the emission bands of p-NH2phO-Zn-t(p-CH

3)PP are red

shifted compared to Zn-t(p-CH3)PP which is due to the elec-

tron donating effect of the amino (ndashNH2) group attached to

the phenolate ion This fluorescence analysis procedure is ofgreat importance in identifying the porphyrin chemosensorsfor selective detection of amine compounds of biological andtechnical interest In addition the possibilities of producing

solid-state solar cells by synthesis of semiconductors withporphyrin compounds have been intensely explored

316 TGADTG Studies

Thermal Analysis of p-OCH3phO-Zn-t-(p-CH3)PP Thermo-gravimetric analyses were performed in an air atmosphere


Table 6 Fluorescence spectral data of axially ligated compoundof X-Zn-t(p-CH

3)PP (X = different phenols as axial ligands) in

methanol solvent using excitation at sim550 nm

Porphyrins 120582max (nm)Zn-t(p-CH3)PP[(C48H36N4Zn1)]

590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)

Figure 3 UV-Visible spectra of p-NH2phO-Zn-t(p-CH

3)PP in

different solvents

at a heating rate of 10∘Cmin to examine thermal stability ofthe compound The TG curve of the complex p-OCH

3phO-

Zn-t-(p-CH3)PP (Figure 5) shows a continuous weight loss

starting from 150∘C to 800∘C when a stable oxide of ZnO isformed The TG curve shows an initial weight loss of about1434 (the theoretical value = 147) observed between140∘C and 170∘C and is attributed to the removal of para-methoxy-phenyl ring as axial group In the range of 200∘Cto 425∘C up to 422 of the mass had been lost due to theloss of tetraphenyl group (the theoretical value = 4239)At 4460∘C up to 6990 (the theoretical value = 7079) ofthe total mass had been lost corresponding to the collapse ofmacrocyclic ligand The organic moiety decomposes furtherwith increasing temperature Further in the range of 450∘Cndash600∘C theweight loss reaches up to 967which is attributedto the removal of pyrrole groups and complete decompositionof macrocyclic ligand and finally ZnO is remained (thetheoretical value = 969)

Simultaneously there were three exothermal peaks at492∘C 563∘C and 580∘C on the DTA curve correspondingto the major weight loss in the ligand H

2-t(p-CH

3)PP

(460∘Cndash580∘C) The small exothermic peak corresponds tothe decomposition of the ligand and the loss of chains of

550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)

Zn-t(p-CH3)PPp-NH2phO-Zn-t(p-CH3)PPexc = 550nm

Figure 4 Fluorescence spectral data of Zn-t(p-CH3)PP and p-

NH2phO-Zn-t(p-CH

3)PP in methanol at excitation 550 nm

600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967

Temperature (smoothed) (∘C)

Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100

Figure 5 TG curve (a) and DTA curve (b) of p-OCH3phO-Zn-t(p-

CH3)PP

the porphyrin ring and the large exothermic peak corre-sponds to the collapse of the porphyrin skeleton

317 Biological Evaluation

Antifungal Activity Antifungal activities of some complexeswere studied against one fungal strain ldquoSclerotium rolfsirdquoIt is concluded that all the synthesized complexes showedoverall good activity against this antifungal strain up to90 (Figures 6(a) 6(b) 6(c) and 6(d)) From the resultsfound (Table 7) it has been concluded that on increasingthe concentration of the complexes the colony diameter ofthe fungus decreases and hence percent inhibition increasesOn doubling the concentration of the complexes the percentinhibition also doubles which shows linear relationshipbetween concentration and percent inhibition The increasein biological activity is due to faster diffusion of metalcomplexes as a whole through the cell membrane or due to


Table 7 In vitro efficacy of axially ligated X-Zn-t(p-CH3)PP (X = different phenols as axial ligand) against the pathogen Sclerotium rolfsiColony diameter of control 119862 = 90mm

Porphyrins Different concentration(ppm) of the complexes

Colony diameter(in mm) at different

concentrations

inhibition119868 = [(119862 minus 119879)119862] lowast 100 atdifferent concentrations

(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)

Figure 6 (a) Antifungal activity of p-NH2phO-Zn-t(p-CH

3)PP (b) antifungal activity of p-OCH

3phO-Zn-t(p-CH

3)PP (c) antifungal activity

of p-NO2phO-Zn-t(p-CH

3)PP and (d) antifungal activity of p-ClphO-Zn-t(p-CH

3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549

Effect of X-ZnII -t(p-CH3)PP human cancer cell lines

Figure 7 In vitro cytotoxicity of p-NO2phO-Zn-t(p-CH

3)PP com-

plexes against human cancer cell lines

combined effect of metal atom and the ligand Such increasedactivity of the metal complexes can be explained on the basisof Overtonersquos concept [46] and Tweedyrsquos chelation theory[47] The lipid membrane that surrounds the cell favors thepassage of only lipid soluble materials due to liphophilicitybeing an important factor which controls the antimicrobialactivity On chelation the polarity of the metal ion will bereduced to a greater extent due to overlap of the ligand orbitaland partial sharing of the positive charge of themetal ionwithdonor groupIn Vitro Cytotoxicity Evaluation of in vitro cytotoxicity of thecorresponding ligand was also observed against four humancancer cell lines namely Breast (MCF-7) Leukemia (THP-1)Prostate (PC-3) and Lung (A549) at different concentrationsby using SRB assay as shown in Figure 7 Dose dependentpercent growth inhibition was observed against all the cancercell lines Among the substituted oxygen donor ligands p-NO2phO-Zn-t(p-CH

3)PP showed prominent activity against

three A549 MCF-7 and THP-1 human cancer cell linesHighest growth percent inhibitionwas observed against Lungcancer cell line and lowest percent growth inhibition wasobserved against Prostate cancer cell line by the ligand Thepercent growth inhibition observed for the ligand was 57 90and 95 against Lung 50 52 and 86 against Breast and 21 41and 84 against leukemia cancer cell lines at 10 50 and 100 120583Mrespectively because the presence of electron-withdrawingnitro group (ndashNO

2) on the phenolic ring in general increases

the antimicrobial activities of the tested metal complexescompared to complexes having no substituent These resultssuggested that metal complexes had effective improvementof bioavailability and electron-withdrawing nitro group hadeffective and direct impact on selective anticancer activitiesHence therefore the ligand p-NO

2phO which is axially

ligated with Zn-t(p-CH3)PP shows overall better activity

than its free base H2-t(p-CH

3)PP and metallated Zn-t(p-

CH3)PP The complex p-NO

2phO-Zn-t(p-CH

3)PP showed

less than 59 growth inhibition against Prostate (PC-3)human cancer cell line

N

N

N

NR

R

R

R Zn

X

Figure 8 Proposed structure of axially ligated zinc(II) porphyrins

4 Conclusion

On the basis of physicochemical and spectral evidences it isfound that all the complexeswith a general formulaX-Zn-t(p-CH3)PP (X = different phenolates as axial ligand) in which

the four-coordinate zinc porphyrin will accept one and onlyone axial ligand in 1 1 molar ratio to form five-coordinatedcomplexes The proposed structure for the complexes underinvestigation with general formula [X-Zn-t(p-CH

3)PP] is

given as Figure 8 Also biological evaluation (antifungal andanticancer activities) of the synthesized complexes showsthat these complexes have potential against fungal growthMoreover for anticancer activity highest growth percentinhibitionwas observed against Lung cancer cell line and low-est percent growth inhibition was observed against Prostatecancer cell line by the ligand

Conflict of Interests

The authors declare that they have no conflict of interests

References

[1] V K Gupta D K Chauhan V K Saini S Agarwal M MAntonijevic and H Lang ldquoA porphyrin based potentiometricsensor for Zn2+ determinationrdquo Sensors vol 3 no 7 pp 223ndash235 2003

[2] C-T Chen ldquoEvolution of red organic light-emitting diodesmaterials and devicesrdquo Chemistry of Materials vol 16 no 23pp 4389ndash4400 2004

[3] O S Wolfbeis ldquoFiber-optic chemical sensors and biosensorsrdquoAnalytical Chemistry vol 78 no 12 pp 3859ndash3873 2006

[4] V K Gupta S Chandra D K Chauhan and RMangla ldquoMem-branes of 5101520-tetrakis(4-methoxyphenyl) porphyrinato-cobalt (TMOPP-Co) (I) as MoO 2minus

4-selective sensorsrdquo Sensors

vol 2 no 5 pp 164ndash173 2002


[5] K I Ozoemena ldquoAnodic oxidation and amperometric sensingof hydrazine at a glassy carbon electrode modified with cobalt(II) phthalocyanine-cobalt (II) tetraphenylporphyrin (CoPc-(CoTPP)4) supramolecular complexrdquo Sensors vol 6 no 8 pp874ndash891 2006

[6] O Ikeda K Yoshinaga and J Lei ldquoNitric oxide detection withglassy carbon electrodes coated with charge-different polymerfilmsrdquo Sensors vol 5 no 4-5 pp 161ndash170 2005

[7] R Purrello A Raudino L Monsu Scolaro A Loisi E Bellac-chio and R Lauceri ldquoTernary porphyrin aggregates and theirchiral memoryrdquo Journal of Physical Chemistry B vol 104 no 46pp 10900ndash10908 2000

[8] H S Cho D H Jeong S Cho et al ldquoPhotophysical propertiesof porphyrin tapesrdquo Journal of the American Chemical Societyvol 124 no 49 pp 14642ndash14654 2002

[9] J Yu X Wang B Zhang Y Weng and L Zhang ldquoProlongedexcited-state lifetime of porphyrin due to the addition ofcolloidal SiO

2to Triton X-100 micellesrdquo Langmuir vol 20 no

5 pp 1582ndash1586 2004[10] S Tangestaninejad M H Habibi V Mirkhani and M

Moghadam ldquoMn (Br8TPPS) supported on Amberlite IRA-400

as a robust and efficient catalyst for alkene epoxidation andalkane hydroxylationrdquo Molecules vol 7 no 2 pp 264ndash2702002

[11] E G Girichev M I Bazanov N Z Mamardashvili and AGjeyzak ldquoElectrochemical and electrocatalytical properties of371317-tetramethyl- 281218-tetrabutylporphyrin in alkalinesolutionrdquoMolecules vol 5 no 6 pp 767ndash774 2000

[12] B Gao Y Chen and Q Lei ldquoHydroxylationof cyclohexanewithmolecular oxygen catalyzed by highly efficient heterogeneousMn(III) porphyrin catalysts prepared by special synthesis andimmobilization methodrdquo Journal of Inclusion Phenomena andMacrocyclic Chemistry vol 74 no 1ndash4 pp 455ndash465 2012

[13] A E OrsquoConnor W M Gallagher and A T Byrne ldquoPorphyrinandnonporphyrin photosensitizers in oncology preclinical andclinical advances in photodynamic therapyrdquo Photochemistryand Photobiology vol 85 no 5 pp 1053ndash1074 2009

[14] M Wathier and M W Grinstaff ldquoSynthesis and propertiesof supramolecular ionic networksrdquo Journal of the AmericanChemical Society vol 130 no 30 pp 9648ndash9649 2008

[15] CMDrain A Varotto and I Radivojevic ldquoSelf-organized por-phyrinic materialsrdquo Chemical Reviews vol 109 no 5 pp 1630ndash1658 2009

[16] D Vlascici E F Cosma E M Pica et al ldquoFree base porphyrinsas ionophores for heavymetal sensorsrdquo Sensors vol 8 no 8 pp4995ndash5004 2008

[17] D Aviezer S Cotton M David et al ldquoPorphyrin analoguesas novel antagonists of fibroblast growth factor and vascu-lar endothelial growth factor receptor binding that inhibitendothelial cell proliferation tumor progression and metasta-sisrdquo Cancer Research vol 60 no 11 pp 2973ndash2980 2000

[18] H Imahori Y Mori and Y Matano ldquoNanostructured artificialphotosynthesisrdquo Journal of Photochemistry and Photobiology Cvol 4 no 1 pp 51ndash83 2003

[19] A Forneli M Planells M A Sarmentero et al ldquoThe role ofpara-alkyl substituents on meso-phenyl porphyrin sensitisedTiO2solar cells control of the eTiO2electrolyte

+ recombinationreactionrdquo Journal of Materials Chemistry vol 18 no 14 pp1652ndash1658 2008

[20] A D Adler F R Longo J D Finarelli J Goldmacher JAssour and L Korsakoff ldquoA simplified synthesis for meso-tetraphenylporphinrdquo Journal of Organic Chemistry vol 32 no2 p 476 1967

[21] K M Kadish K M Smith and R Guilard The PorphyrinHandbook Academic Press San Diego Calif USA 2000

[22] K Saito Y Kashiwagi K Ohkubo and S Fukuzumi ldquoAnextremely long-lived charge-separated state of zinc tetraphenyl-porphyrin coordinatedwith pyridylnaphthalene-diimiderdquo Jour-nal of Porphyrins and Phthalocyanines vol 10 no 12 pp 1371ndash1379 2006

[23] V K K Praneeth F Paulat T C Berto et al ldquoElectronic struc-ture of six-coordinate iron(III)-porphyrin NO adducts theelusive iron(III)-NO(radical) state and its influence on theproperties of these complexesrdquo Journal of the American Chemi-cal Society vol 130 no 46 pp 15288ndash15303 2008

[24] A S Semeikin O I Koifman and B D Berezin ldquoSynthesis oftetraphenylporphins with active groups in the phenyl rings 1Preparation of tetrakis(4-aminophenyl)porphinrdquo Chemistry ofHeterocyclic Compounds vol 18 no 10 pp 1046ndash1047 1982

[25] K M Kadish K M Smith and R Guilard ldquoBiochemistry andbinding activation of small moleculesrdquo inThe Porphyrin Hand-book Academic Press New York NY USA 1999

[26] M Nappa and J S Valentine ldquoThe influence of axial ligandson metalloporphyrin visible absorption spectra Complexes oftetraphenylporphinatozincrdquo Journal of the American ChemicalSociety vol 100 no 16 pp 5075ndash5080 1978

[27] M-Y R Wang and B M Hoffman ldquoSystematic trends inmetalloporphyrin optical spectrardquo Journal of the AmericanChemical Society vol 106 no 15 pp 4235ndash4240 1984

[28] I Stojiljkovic B D Evavold and V Kumar ldquoAntimicrobialproperties of porphyrinsrdquo Expert Opinion on InvestigationalDrugs vol 10 no 2 pp 309ndash320 2001

[29] K Rajesh A K Rahiman K S Bharathi S Sreedaran V Gan-gadevi and V Narayanan ldquoSpectroscopic redox and biologicalstudies of push-pull porphyrins and their metal compleesrdquoBulletin of the Korean Chemical Society vol 31 no 9 pp 2656ndash2664 2010

[30] J Bozja J Sherrill SMichielsen and I Stojiljkovic ldquoPorphyrin-based light-activated antimicrobial materialsrdquo Journal of Poly-mer Science Part A vol 41 no 15 pp 2297ndash2303 2003

[31] R A Sanchez-Delgado K Lazardi L Rincon and J AUrbina ldquoToward a novel metal-based chemotherapy againsttropical diseases 1 Enhancement of the efficacy of clotrimazoleagainst Trypanosoma cruzi by complexation to ruthenium inRuCl2(clotrimazole)

2rdquo Journal of Medicinal Chemistry vol 36

pp 2041ndash2043 1993[32] M T H Tarafder K T Jin K A Crouse A M Ali B M

Yamin andH-K Fun ldquoCoordination chemistry and bioactivityof Ni2+ Cu2+ Cd2+ and Zn2+ complexes containing biden-tate schiff bases derived from S-benzyldithiocarbazate andthe X-ray crystal structure of bis[S-benzyl-120573-N-(5-methyl-2-furylmethylene)dithiocarbazato]cadmium(II)rdquoPolyhedron vol21 no 25-26 pp 2547ndash2554 2002

[33] J Sheikh H Juneja V Ingle P Ali and T B Hadda ldquoSynthesisand in vitro biology of Co(II) Ni(II) Cu(II) and Zinc(II) com-plexes of functionalized beta-diketone bearing energy buriedpotential antibacterial and antiviral OO pharmacophore sitesrdquoJournal of Saudi Chemical Society vol 17 pp 269ndash276 2013

[34] J R Platt andH B Klevens ldquoSpectroscopy of organicmoleculesin the vacuum ultravioletrdquo Reviews of Modern Physics vol 16no 3-4 pp 182ndash223 1944


[35] G P Gurinovich A N Sevchenko and K N SolovyevldquoSpectroscopy of chlorophyll and alliedcompoundsrdquo Nauka iTekhnika In press

[36] L A NafieM Pezolet andW L Peticolas ldquoOn the origin of theintensity of the resonant raman bands of differing polarizationin heme proteinsrdquo Chemical Physics Letters vol 20 no 6 pp563ndash568 1973

[37] J M Vincent ldquoDistortion of fungal hyphaelig in the presence ofcertain inhibitorsrdquo Nature vol 159 no 4051 p 850 1947

[38] A Thiantanawat B J Long and A M Brodie ldquoSignalingpathways of apoptosis activated by aromatase inhibitors andantiestrogensrdquo Cancer Research vol 63 no 22 pp 8037ndash80502003

[39] X Tong S Lin M Fujii and D-X Hou ldquoEchinocystic acidinduces apoptosis in HL-60 cells through mitochondria-mediated death pathwayrdquo Cancer Letters vol 212 no 1 pp 21ndash32 2004

[40] H Scheer and J J Katz ldquoNuclear magnetic resonance spec-troscopy of porphyrins and metalloporphyrinsrdquo in Porphyrinsand Metalloporphyrins K M Smith Ed p 399 ElsevierAmsterdam The Netherlands 1975

[41] E Fagadar-Cosma C Enache I Armeanu et al ldquoThe influenceof pH over topography and spectroscopic properties of silicahybrid materials embedding meso-tetratolylporphyrinrdquo Mate-rials Research Bulletin vol 44 no 2 pp 426ndash431 2009

[42] K Schweiger M Goldner H Huckstadt and H ZHomborg ldquoSynthese and Eigen Schaften Von cis Diacid-ophthalocyaninato(2-)thallaton(III) kristallstruktur von Tetra-(n-butyl)ammonium-cisdinitro(OO1015840)-and-cis-dichlorophthal-ocyaninato(2-)thallat(III)rdquo Zeitschrift fur Anorganische undAllgemeine Chemie vol 625 no 10 pp 1693ndash1699 1999

[43] R C Dougherty in Biochemical Applications ofMass Spectrom-etry G R Waller Ed vol 6 p 1288 John Wiley amp Sons NewYork NY USA 1972

[44] C Timiriazeff ldquoColourless chlorophyllrdquoNature vol 32 no 824p 342 1885

[45] J-P Strachan S Gentemann J Seth et al ldquoEffects of orbitalordering on electronic communication in multiporphyrinarraysrdquo Journal of the American Chemical Society vol 119 no46 pp 11191ndash11201 1997

[46] N Dharmaraj P Viswanathamurthi and K Natarajan ldquoRuthe-nium(II) complexes containing bidentate Schiff bases and theirantifungal activityrdquo Transition Metal Chemistry vol 26 no 1-2pp 105ndash109 2001

[47] L Mishra and V K Singh ldquoCo(ll) Ni(ll) and Cu(lI) and Zn(lI)complexes with Schiff bases derived from 2-aminobenzimida-zoles and pyrazolycarboxaldehyderdquo Indian Journal of Chem-istry vol 32 p 446 1993

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


the efficiency of energy or electron transfer processes [2324] This ability of metalloporphyrins to attach additionalligand (extra coordination) determines their role in enzymeand catalytic processes Mono- or bidentate complexes formdepending on the system of substituent in the porphyrinmacrocycle central ion or the nature and concentration ofthe extra ligand The reactions of extra coordination attractattention on both theoretical and experimental researches[25] Also the detailed studies on the solvation and axial lig-ation properties of ZnTPP have been reported [26 27]Theseinvestigations have shed light on how axial ligands inducechanges in the spectral absorption features and the electro-chemistry of metalloporphyrins The ability for numerouschemical modifications and the large number of differentmechanisms by which porphyrins affect microbial and viralpathogens place porphyrins into a group of compounds withan outstanding potential for discovery of novel agents pro-cedures andmaterials active against pathogenicmicroorgan-isms [28] Metalloporphyrins are the basis of new antifungalantiparasitic and anticancer drugs because modification ofthe porphyrin periphery confers qualitatively a new spectrumof activities to metalloporphyrins [29 30] Metal complexesare well known to accelerate drug action and the efficiency ofa therapeutic agent can often be enhanced upon coordinationwith a metal ion [31] Of particular interest metal ions suchas zinc which is a natural component of insulin required forthe regulation of sugarmetabolism and it is also incorporatedinto the catalytic proteins to act as a metalloenzyme thatfacilitate a multitude of chemical reactions needed for lifeZn(II) metal complexes with different ligands show overallgood potential for antibacterial antifungal antioxidant andanticancer activities [32 33] Zinc also forms low molecularweight complexes and therefore proves to bemore beneficialagainst several diseases Various biological aspects of themetal-based drugsligands entirely depend on the ease ofcleaving the bond between the metal ion and the ligand Asa consequence it is essential to understand the relationshipbetween ligand and the metal in biological systemsWith thisobjective we aimed at synthesis spectroscopic characteriza-tion and biological studies of axial zinc(II)-5101520-meso-tetra(para-methylphenyl)porphyrins with different phenolsas axial ligand

2 Experimental

21 Materials and Instruments All the chemicals were ofanalytical grade and used as received unless otherwise notedPyrrole (Fluka Switzerland) was distilled at room tempera-ture over potassium hydroxide (KOH) pellets under reducedpressure before use p-Tolualdehyde (p-methylbenzaldehyde)(Aldrich USA) propionic acid (Qualigens India) silica gel(60ndash120mesh) and silica gel (TLC grade particle size =75 120583 (Merck Germany) aluminum oxide (basic) for col-umn chromatography (Fluka Switzerland) and zinc acetate(Zn(OAc)

2sdot2H2O) (E Merck India) were used as supplied

Organic solvents were degassed by purging with prepurifiednitrogen gas and dried before use The various phenols usedwere of AR grade (Sisco Research Laboratories Pvt Ltd) andused without further purification

The optical absorption spectra of the compounds wererecorded on a Hitachi U-3400 Lambda 35 UV-Vis spec-trophotometer and Elico spectral treats UV-Vis spectrometerusing a pair of matched quartz cells of 10mm path lengthat an ambient temperature The oscillator strength (f ) of thetransitions in absorption spectra was calculated from theexpression [34]

119891 = 433 times 10

minus9120576Δ]12

(1)

where 120576 is themolar absorption coefficient in dm3molminus1 cmminus1and Δ]

12is the full width at half maximum in cmminus1 IR

spectra of complexes over the region 4000ndash400 cmminus1 wererecorded on PERKIN ELMER 580 B spectrophotometer atroom temperature using KBr discs or Nujol mulls whichconfirms the (M-N) and (M-L) vibration [35 36] The1H NMR spectra were recorded on a Bruker Avance II 400(MHz) NMR spectrometer in CDCl

3using tetramethylsilane

(TMS) as internal standard Porphyrin solutions (05mL) of10minus2 to 10minus3m in CDCl

3were used for 1HNMR studies Car-

bon hydrogen and nitrogenwere analyzedmicroanalyticallyusing CHNS analyzer Lecomodel 932 USA at a temperatureof about 1000∘C using helium as carrier gas and oxygenfor combustion The MALDI mass spectra were recorded inthe electron-impact mode on a Finnigan 3300 spectrometerusing chloroform or methanol as solvent The steady statefluorescence measurements were performed on synergy MXBiotek Multimode reader using a quartz cell of 1 cm pathlength at ambient temperature The thermogravimetric anal-yses (TGA) and differential thermal analyses (DTA) wereperformed on a Linseis STA PT-1000 in air atmosphere ata heating rate of 10∘Cmin The right angle detection wasemployed for monitoring the fluorescence

22 Biological Studies

221 Antifungal Studies The in vitro antifungal activity hasbeen done by disc diffusion method (DDM) against thepathogen and in vitro cytotoxicity against human cancer celllines In vitro antifungal activity of some of the investigatedcompounds was tested by agar plate technique against thepathogen ldquoSclerotium rolfsirdquo by the poisoned food methodusing potato dextrose agar (PDA) (glucose 20 g starch 20 gand agar-agar 20 g in 1000mL distilled water) nutrient as themedium Solution of the test compounds inDMSO (100 ppm200 ppm and 300 ppm concentrations) was prepared andmixed with the PDA The medium was then poured intosterilized Petri plates and the spores of fungi were placedon the medium with the help of inoculumrsquos needle insidelaminar flow The plates were inoculated with seven-day-oldculture of the pathogen by placing 2mm bit of the compoundunder investigation with different concentration in the centreof plates The inoculated plates were incubated at 27∘C for 5days The linear growth of fungus in control and treatmentwas recorded at different concentrations of the complexesafter 5 daysThegrowth of ldquoSclerotium rolfsirdquo over controlwascalculated as per Vincent [37]

inhibition (119868) = (119862 minus 119879)119862

times 100(2)





2incubator (Heraeus





2t(p-CH


2-t(p-CH

3)PP


2-t(p-CH

3)PP


3))430





3) at 2855


Found C 8611 H 589 N 842


3)PP] H

2-t(p-CH

3)PP (20mg





3)PP]


3)) 432 5642 6093 1H NMR

(CDCl3) 865 (s8H 120573py-H) 775 (d8HH

119898) 806 (d8HH

119900)




C48H36N4Zn1() C 7839 H 493 N 761 Found C 7846

H 499 N 772


3)PP] It is as fol-

lows


3)PP (3)











2-t(p-CH




2-t(p-CH

3)PP the resonance


2TPP The





2phO-Zn-



3)PP


NHN

NHN

Propionic acid

Refluxing (12h)


(a)


N

N N

NCH3

CH3

CH3

H3C

H3C

H3C Zn


(b)

(CH3OH 10mL)

Reflux2hrs


(CH3OH 10mL)



NN

NN

CH3

CH3

CH3

H3C Zn



(pure)(c)


-Oph

120572-Naphthol

CHO

+

NH

CH3

44CH3 + X

CH3

CH3

CH3

CH3

X

N

N N

NZn

X


2hrs

(crude)

Extr

actio

n

chlo

rofo

rm as

an el

uent



2NN

AOH

and


o- m- and p-OCH3Oph

o- m- and p-NO2Oph

o- m- and p-ClOph

24-Dichlorophenol








2-t(p-CH

3)PP The methyl


2t(p-CH

3)PP revealed that



3 ndashOCH

3 and ndashNH

2


3)PP and H

2t(p-CH

3)PP complexes










886 (s) minus277 (s) 811(d 8H H119900)

756(d 8H H119898) 264(s 12H Hme)


865 (s) mdash 806(d 8H H119900)

775(m 8H H119898) 269(s 12H Hme)


899 (s) mdash 841(d 10H H119900)

776(d 11H H119898119901

) 271(s 12H Hme)


92 (s) mdash 829(d 10H H119900)

792(d 10H H119898) 29(s 12H Hme)


893 (s) mdash 822(d 10H H119900)

766(d 10H H119898)

231(s 12H Hme)336(s 3H Home)


890 (s) mdash 826(d 10H H119900)

769(m 10H H119898)

236(s 12H Hme)509(s 2H HNH2


94 (s) mdash 833(d 10H H119900)

796(d 10H H119898) 33(s 12H Hme)


901 (s) mdash 839(d 10H H119900)

792(d 10H H119898) 265(s 12H Hme)


(ppm)9 8 7 6 5 4 3 2 1 0

Methyl-H

lowast lowast

lowast

lowast

Phmeso

Phmeso

839(d10HHo)

792(d10HHm)

Pyrrole-H901(s8H)

Inte

rnal

1000

1129

1256

0910

1681

13622

1257


3)PP in








12)


2Cl2

(ppm)9 8 7 6 5 4 3 2 1 0

lowast lowast

lowast

Inte

rnal

1000

1129

1256

0910

1681

13622

1257

Methyl-H

Phmeso

Phmeso

822(d10HHo)766(d10HHm)

Pyrrole-H893(s8H)

-OCH3-H


3)PP in





3gt CH

2Cl2gt CCl

4 As in the




3 CH2Cl2 and CCl



3 CH2Cl2 and CCl

4was observed






430 (5986) 9894 516 553 592 649


432 (5824) (9953) 5642 (4218) 78936093 (4160)


4302 (5771) (9979) 5638 (4312) 78515986 (4289)


4314 (5798) (1008) 5640 (4418) 82946004 (4389)


432 (5833) (9808) 5694 (4484) 82626096 (4338)


4319 (5845) (9789) 5702 (4521) 78936083 (4432)


4324 (5808) (9841) 567 (4448) 8224604 (4392)


4334 (5806) (998) 5724 (4527) 79626063 (4486)


4332 (5696) (9924) 5704 (4456) 69866051 (4412)


4339 (5859) (9866) 5709 (4432) 69946046 (4398)


431 (5964) (9871) 565 (4643) 7621596 (4431)


4318 (5839) (9864) 564 (4682) 7609588 (4432)


4316 (5969) (9869) 564 (4861) 7606587 (4743)


428 (5942) (9989) 546 (4549) 8542581 (4431)


427 (5841) (9952) 546 (4643) 8469580 (4428)


427 (5872) (9956) 546 (4516) 8428578 (4314)


426 (5646) (10144) 547 (4569) 8723575 (4321)


425 (5781) (9925) 548 (4439) 7819579 (4532)


425 (5841) (9986) 548 (4598) 7852579 (4514)



2-t(p-CH






2-t(p-CH






(cmminus1)



12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536


MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695


2phO-Zn-t(p-CH





3phO-Zn-t(p-CH














1rarr


2to S1is rapid so





3)PP The


3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in




∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





2incubator (Heraeus





2t(p-CH


2-t(p-CH

3)PP


2-t(p-CH

3)PP


3))430





3) at 2855


Found C 8611 H 589 N 842


3)PP] H

2-t(p-CH

3)PP (20mg





3)PP]


3)) 432 5642 6093 1H NMR

(CDCl3) 865 (s8H 120573py-H) 775 (d8HH

119898) 806 (d8HH

119900)




C48H36N4Zn1() C 7839 H 493 N 761 Found C 7846

H 499 N 772


3)PP] It is as fol-

lows


3)PP (3)











2-t(p-CH




2-t(p-CH

3)PP the resonance


2TPP The





2phO-Zn-



3)PP


NHN

NHN

Propionic acid

Refluxing (12h)


(a)


N

N N

NCH3

CH3

CH3

H3C

H3C

H3C Zn


(b)

(CH3OH 10mL)

Reflux2hrs


(CH3OH 10mL)



NN

NN

CH3

CH3

CH3

H3C Zn



(pure)(c)


-Oph

120572-Naphthol

CHO

+

NH

CH3

44CH3 + X

CH3

CH3

CH3

CH3

X

N

N N

NZn

X


2hrs

(crude)

Extr

actio

n

chlo

rofo

rm as

an el

uent



2NN

AOH

and


o- m- and p-OCH3Oph

o- m- and p-NO2Oph

o- m- and p-ClOph

24-Dichlorophenol








2-t(p-CH

3)PP The methyl


2t(p-CH

3)PP revealed that



3 ndashOCH

3 and ndashNH

2


3)PP and H

2t(p-CH

3)PP complexes










886 (s) minus277 (s) 811(d 8H H119900)

756(d 8H H119898) 264(s 12H Hme)


865 (s) mdash 806(d 8H H119900)

775(m 8H H119898) 269(s 12H Hme)


899 (s) mdash 841(d 10H H119900)

776(d 11H H119898119901

) 271(s 12H Hme)


92 (s) mdash 829(d 10H H119900)

792(d 10H H119898) 29(s 12H Hme)


893 (s) mdash 822(d 10H H119900)

766(d 10H H119898)

231(s 12H Hme)336(s 3H Home)


890 (s) mdash 826(d 10H H119900)

769(m 10H H119898)

236(s 12H Hme)509(s 2H HNH2


94 (s) mdash 833(d 10H H119900)

796(d 10H H119898) 33(s 12H Hme)


901 (s) mdash 839(d 10H H119900)

792(d 10H H119898) 265(s 12H Hme)


(ppm)9 8 7 6 5 4 3 2 1 0

Methyl-H

lowast lowast

lowast

lowast

Phmeso

Phmeso

839(d10HHo)

792(d10HHm)

Pyrrole-H901(s8H)

Inte

rnal

1000

1129

1256

0910

1681

13622

1257


3)PP in








12)


2Cl2

(ppm)9 8 7 6 5 4 3 2 1 0

lowast lowast

lowast

Inte

rnal

1000

1129

1256

0910

1681

13622

1257

Methyl-H

Phmeso

Phmeso

822(d10HHo)766(d10HHm)

Pyrrole-H893(s8H)

-OCH3-H


3)PP in





3gt CH

2Cl2gt CCl

4 As in the




3 CH2Cl2 and CCl



3 CH2Cl2 and CCl

4was observed






430 (5986) 9894 516 553 592 649


432 (5824) (9953) 5642 (4218) 78936093 (4160)


4302 (5771) (9979) 5638 (4312) 78515986 (4289)


4314 (5798) (1008) 5640 (4418) 82946004 (4389)


432 (5833) (9808) 5694 (4484) 82626096 (4338)


4319 (5845) (9789) 5702 (4521) 78936083 (4432)


4324 (5808) (9841) 567 (4448) 8224604 (4392)


4334 (5806) (998) 5724 (4527) 79626063 (4486)


4332 (5696) (9924) 5704 (4456) 69866051 (4412)


4339 (5859) (9866) 5709 (4432) 69946046 (4398)


431 (5964) (9871) 565 (4643) 7621596 (4431)


4318 (5839) (9864) 564 (4682) 7609588 (4432)


4316 (5969) (9869) 564 (4861) 7606587 (4743)


428 (5942) (9989) 546 (4549) 8542581 (4431)


427 (5841) (9952) 546 (4643) 8469580 (4428)


427 (5872) (9956) 546 (4516) 8428578 (4314)


426 (5646) (10144) 547 (4569) 8723575 (4321)


425 (5781) (9925) 548 (4439) 7819579 (4532)


425 (5841) (9986) 548 (4598) 7852579 (4514)



2-t(p-CH






2-t(p-CH






(cmminus1)



12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536


MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695


2phO-Zn-t(p-CH





3phO-Zn-t(p-CH














1rarr


2to S1is rapid so





3)PP The


3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in




∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NHN

NHN

Propionic acid

Refluxing (12h)


(a)


N

N N

NCH3

CH3

CH3

H3C

H3C

H3C Zn


(b)

(CH3OH 10mL)

Reflux2hrs


(CH3OH 10mL)



NN

NN

CH3

CH3

CH3

H3C Zn



(pure)(c)


-Oph

120572-Naphthol

CHO

+

NH

CH3

44CH3 + X

CH3

CH3

CH3

CH3

X

N

N N

NZn

X


2hrs

(crude)

Extr

actio

n

chlo

rofo

rm as

an el

uent



2NN

AOH

and


o- m- and p-OCH3Oph

o- m- and p-NO2Oph

o- m- and p-ClOph

24-Dichlorophenol








2-t(p-CH

3)PP The methyl


2t(p-CH

3)PP revealed that



3 ndashOCH

3 and ndashNH

2


3)PP and H

2t(p-CH

3)PP complexes










886 (s) minus277 (s) 811(d 8H H119900)

756(d 8H H119898) 264(s 12H Hme)


865 (s) mdash 806(d 8H H119900)

775(m 8H H119898) 269(s 12H Hme)


899 (s) mdash 841(d 10H H119900)

776(d 11H H119898119901

) 271(s 12H Hme)


92 (s) mdash 829(d 10H H119900)

792(d 10H H119898) 29(s 12H Hme)


893 (s) mdash 822(d 10H H119900)

766(d 10H H119898)

231(s 12H Hme)336(s 3H Home)


890 (s) mdash 826(d 10H H119900)

769(m 10H H119898)

236(s 12H Hme)509(s 2H HNH2


94 (s) mdash 833(d 10H H119900)

796(d 10H H119898) 33(s 12H Hme)


901 (s) mdash 839(d 10H H119900)

792(d 10H H119898) 265(s 12H Hme)


(ppm)9 8 7 6 5 4 3 2 1 0

Methyl-H

lowast lowast

lowast

lowast

Phmeso

Phmeso

839(d10HHo)

792(d10HHm)

Pyrrole-H901(s8H)

Inte

rnal

1000

1129

1256

0910

1681

13622

1257


3)PP in








12)


2Cl2

(ppm)9 8 7 6 5 4 3 2 1 0

lowast lowast

lowast

Inte

rnal

1000

1129

1256

0910

1681

13622

1257

Methyl-H

Phmeso

Phmeso

822(d10HHo)766(d10HHm)

Pyrrole-H893(s8H)

-OCH3-H


3)PP in





3gt CH

2Cl2gt CCl

4 As in the




3 CH2Cl2 and CCl



3 CH2Cl2 and CCl

4was observed






430 (5986) 9894 516 553 592 649


432 (5824) (9953) 5642 (4218) 78936093 (4160)


4302 (5771) (9979) 5638 (4312) 78515986 (4289)


4314 (5798) (1008) 5640 (4418) 82946004 (4389)


432 (5833) (9808) 5694 (4484) 82626096 (4338)


4319 (5845) (9789) 5702 (4521) 78936083 (4432)


4324 (5808) (9841) 567 (4448) 8224604 (4392)


4334 (5806) (998) 5724 (4527) 79626063 (4486)


4332 (5696) (9924) 5704 (4456) 69866051 (4412)


4339 (5859) (9866) 5709 (4432) 69946046 (4398)


431 (5964) (9871) 565 (4643) 7621596 (4431)


4318 (5839) (9864) 564 (4682) 7609588 (4432)


4316 (5969) (9869) 564 (4861) 7606587 (4743)


428 (5942) (9989) 546 (4549) 8542581 (4431)


427 (5841) (9952) 546 (4643) 8469580 (4428)


427 (5872) (9956) 546 (4516) 8428578 (4314)


426 (5646) (10144) 547 (4569) 8723575 (4321)


425 (5781) (9925) 548 (4439) 7819579 (4532)


425 (5841) (9986) 548 (4598) 7852579 (4514)



2-t(p-CH






2-t(p-CH






(cmminus1)



12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536


MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695


2phO-Zn-t(p-CH





3phO-Zn-t(p-CH














1rarr


2to S1is rapid so





3)PP The


3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in




∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






886 (s) minus277 (s) 811(d 8H H119900)

756(d 8H H119898) 264(s 12H Hme)


865 (s) mdash 806(d 8H H119900)

775(m 8H H119898) 269(s 12H Hme)


899 (s) mdash 841(d 10H H119900)

776(d 11H H119898119901

) 271(s 12H Hme)


92 (s) mdash 829(d 10H H119900)

792(d 10H H119898) 29(s 12H Hme)


893 (s) mdash 822(d 10H H119900)

766(d 10H H119898)

231(s 12H Hme)336(s 3H Home)


890 (s) mdash 826(d 10H H119900)

769(m 10H H119898)

236(s 12H Hme)509(s 2H HNH2


94 (s) mdash 833(d 10H H119900)

796(d 10H H119898) 33(s 12H Hme)


901 (s) mdash 839(d 10H H119900)

792(d 10H H119898) 265(s 12H Hme)


(ppm)9 8 7 6 5 4 3 2 1 0

Methyl-H

lowast lowast

lowast

lowast

Phmeso

Phmeso

839(d10HHo)

792(d10HHm)

Pyrrole-H901(s8H)

Inte

rnal

1000

1129

1256

0910

1681

13622

1257


3)PP in








12)


2Cl2

(ppm)9 8 7 6 5 4 3 2 1 0

lowast lowast

lowast

Inte

rnal

1000

1129

1256

0910

1681

13622

1257

Methyl-H

Phmeso

Phmeso

822(d10HHo)766(d10HHm)

Pyrrole-H893(s8H)

-OCH3-H


3)PP in





3gt CH

2Cl2gt CCl

4 As in the




3 CH2Cl2 and CCl



3 CH2Cl2 and CCl

4was observed






430 (5986) 9894 516 553 592 649


432 (5824) (9953) 5642 (4218) 78936093 (4160)


4302 (5771) (9979) 5638 (4312) 78515986 (4289)


4314 (5798) (1008) 5640 (4418) 82946004 (4389)


432 (5833) (9808) 5694 (4484) 82626096 (4338)


4319 (5845) (9789) 5702 (4521) 78936083 (4432)


4324 (5808) (9841) 567 (4448) 8224604 (4392)


4334 (5806) (998) 5724 (4527) 79626063 (4486)


4332 (5696) (9924) 5704 (4456) 69866051 (4412)


4339 (5859) (9866) 5709 (4432) 69946046 (4398)


431 (5964) (9871) 565 (4643) 7621596 (4431)


4318 (5839) (9864) 564 (4682) 7609588 (4432)


4316 (5969) (9869) 564 (4861) 7606587 (4743)


428 (5942) (9989) 546 (4549) 8542581 (4431)


427 (5841) (9952) 546 (4643) 8469580 (4428)


427 (5872) (9956) 546 (4516) 8428578 (4314)


426 (5646) (10144) 547 (4569) 8723575 (4321)


425 (5781) (9925) 548 (4439) 7819579 (4532)


425 (5841) (9986) 548 (4598) 7852579 (4514)



2-t(p-CH






2-t(p-CH






(cmminus1)



12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536


MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695


2phO-Zn-t(p-CH





3phO-Zn-t(p-CH














1rarr


2to S1is rapid so





3)PP The


3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in




∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






430 (5986) 9894 516 553 592 649


432 (5824) (9953) 5642 (4218) 78936093 (4160)


4302 (5771) (9979) 5638 (4312) 78515986 (4289)


4314 (5798) (1008) 5640 (4418) 82946004 (4389)


432 (5833) (9808) 5694 (4484) 82626096 (4338)


4319 (5845) (9789) 5702 (4521) 78936083 (4432)


4324 (5808) (9841) 567 (4448) 8224604 (4392)


4334 (5806) (998) 5724 (4527) 79626063 (4486)


4332 (5696) (9924) 5704 (4456) 69866051 (4412)


4339 (5859) (9866) 5709 (4432) 69946046 (4398)


431 (5964) (9871) 565 (4643) 7621596 (4431)


4318 (5839) (9864) 564 (4682) 7609588 (4432)


4316 (5969) (9869) 564 (4861) 7606587 (4743)


428 (5942) (9989) 546 (4549) 8542581 (4431)


427 (5841) (9952) 546 (4643) 8469580 (4428)


427 (5872) (9956) 546 (4516) 8428578 (4314)


426 (5646) (10144) 547 (4569) 8723575 (4321)


425 (5781) (9925) 548 (4439) 7819579 (4532)


425 (5841) (9986) 548 (4598) 7852579 (4514)



2-t(p-CH






2-t(p-CH






(cmminus1)



12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536


MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695


2phO-Zn-t(p-CH





3phO-Zn-t(p-CH














1rarr


2to S1is rapid so





3)PP The


3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in




∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




(cmminus1)



12)

Q (1 0) Q (0 0) B-band Q-bandQ (1 0)


MtOH 4359 714(5638) 45489

589 925(4724) 51621

604 531(4604) 0140635 0206755

CHCl34339 437

(5329) 234585709 1096

(4749) 534036046 532(4598) 0044387 0253434

CH2Cl24328 542

(5261) 186095684 679

(4896) 63885601 740(4423) 00436727 01878264

CCl4430 631

(5594) 423525601 594

(4726) 51764586 447(4412) 0115715 01331380


MtOH 4334 615(5964) 71749

564 459(4643) 47858

592 525(4428) 019106399 00951163

CHCl3425 750

(5781) 58129548 455

(4439) 32674579 549(4532) 01807739 00643726

CH2Cl2424 857

(5536) 39894546 426

(4552) 41085573 503(4561) 014803905 00757845

CCl44228 820

(5536) 39894542 561

(4742) 55227568 511(4431) 01416476 01341536


MtOH 429 686(5389) 29681

584 485(4643) 49061

6162 555(4222) 00881638 01030306

CHCl3427 770

(5872) 66534546 426

(4643) 49061580 463(4428) 02218310 00904969

CH2Cl24278 607

(5418) 318935448 470

(4549) 418895774 367(4431) 00838246 00852483

CCl44244 766

(5569) 434155429 540

(4321) 244935402 584(4249) 01439980 00572695


2phO-Zn-t(p-CH





3phO-Zn-t(p-CH














1rarr


2to S1is rapid so





3)PP The


3)PP with p-NH

2phO-Zn-t(p-CH

3)PP in




∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



∙∙

∙∙

N

O

NN

N

Zn




](C=C)(cmminus1)

](C=N)(cmminus1)

](CH3)(cmminus1)




3446 2964 1350 1650 1589 2855 mdash mdash


mdash 2963 1349 1658 1594 2849 482 mdash


mdash 2963 1351 1654 1590 2851 473 519


mdash 2964 1350 1649 1586 2859 481 526]1(CndashH) = 2850




mdash 2963 1351 1646 1583 2856 464 521 ]1(NH2)sym = 3290

]2(NH2)asym = 3356


mdash 2963 1350 1658 1592 2851 483 518 ]1(NO2)sym = 1344

]2(NO2)asym = 1527


mdash 2963 1349 1659 1594 2846 476 517


mdash 2951 1346 1642 1580 2862 468 519





C54H41N4ZnO82839(82829)

7829(7830)

499(499)

676(676)


C58H43N4ZnO87890(87896)

7931(7917)

494(493)

638(637)


C54H43N5ZnO84339(84446)

7681(7685)

513(514)

83(830)


C55H43N4ZnO285853(85849)

7694(7677)

505(503)

653(651)


C54H40N4ZnOCl 86295(86290)

7516(7508)

467(467)

649(649)


C54H39N4ZnOCl289739(89730)

7227(7236)

438(439)

624(625)


3)PP are red





316 TGADTG Studies







590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






590 640


612 660

1000

0800

0600

0400

0200

0800

0600

0400

0200

550 600 650 750 750

120582 (nm)

120576(d

m3m

olminus1cm

minus1)

420 430 440 450

Soret (B)-band

Q(10)Q(00)Q-bands

(MtOH)(CHCl3)

(CH2Cl2)(CCl4)


3)PP in

different solvents


3phO-




2-t(p-CH

3)PP


550 600 650 700 750 800

0

20

40

60

80

100

120

Wavelength (nm)

Inte

nsity

(au

)



NH2phO-Zn-t(p-CH


600

500

400

300

200

100

600 700 800500400300200100

600 700 800500400300200100

Hea

t flow

(sm

ooth

ed) (

mJs

)

dM-r

el (

) (a)

(b)

1582∘C-14344085∘C-422

4460∘C-6990

5835∘C-967


Temperature (∘C)

0

minus20

minus40

minus60

minus80

minus100


CH3)PP








concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





concentrations


(ppm)


100200300

5262388728

415356816888


100200300

49124025313

45455276522


100200300

5121871162

433375698708


100200300

48365255

466659447166


100200300

37521121275

5833765285

(a) (b)

(c) (d)



3phO-Zn-t(p-CH




3)PP


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


120

100

80

60

40

20

010120583M 50120583M 100120583M 1120583M 1120583M 1120583M 20120583M

Gro

wth

inhi

bitio

ns (

)

Pacli

tax

Mito

myc

in

Adria

myc

in

5-F

U

MCF-7THP-1

PC-3A549



3)PP com-












2phO-Zn-t(p-CH

3)PP showed


N

N

N

NR

R

R

R Zn

X


4 Conclusion



3)PP] is




References



































































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 and Spectroscopic and Biological...

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Transcript of Research Article Synthesis and Spectroscopic and Biological...