Zinc(II) Complex of Meso-Tetraphenylporphyrin with 4-Methoxyaniline: Crystal Structure and Antimicrobial Activities of 4-Methoxyaniline-5, 10, 15, 20-Tetraphenyl-Porphyrinatozinc (II)

Article abstract of DOI:10.1080/15533174.2014.988813

4-Methoxyaniline-5,10,15,20-tetraphenylporphyrinatozinc(II), [(ZnTPP(MOAN)] 1 was synthesized (MOAN = 4-methoxyaniline) and characterized by elemental analysis and spectroscopic techniques. The molecular structure of 1 was determined by single-crystal X-r

Full text of DOI:10.1080/15533174.2014.988813

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Zinc(II) complex of meso-tetraphenylporphyrin with 4-
methoxyaniline: Crystal structure and antimicrobial
activities of 4-methoxyaniline-5, 10, 15, 20-
tetraphenyl-porphyrinatozinc (II)
Joshua A. Obaleyea, Adedibu C. Tellaa, Gabriel K. Obiyenwaa, Nzikahyel Simonab & Margaret
D. Olawalea
a Department of Chemistry, P.M.B.1515, University of Ilorin, Nigeria
b Department of Chemistry, University of Uyo, Nigeria.
Accepted author version posted online: 31 Jul 2015.
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To cite this article: Joshua A. Obaleye, Adedibu C. Tella, Gabriel K. Obiyenwa, Nzikahyel Simon & Margaret D. Olawale
(2015): Zinc(II) complex of meso-tetraphenylporphyrin with 4-methoxyaniline: Crystal structure and antimicrobial activities
of 4-methoxyaniline-5, 10, 15, 20-tetraphenyl-porphyrinatozinc (II), Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, DOI: 10.1080/15533174.2014.988813
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Zinc(II) complex of meso-tetraphenylporphyrin with 4-methoxyaniline: Crystal structure
and antimicrobial activities of 4-methoxyaniline-5, 10, 15, 20-tetraphenyl-porphyrinatozinc
(II)
Joshua A. Obaleye 1* ; Adedibu C. Tella1 ; Gabriel K. Obiyenwa1 ; Nzikahyel Simon1,2
Margaret D.Olawale1
;
1Department of Chemistry, P.M.B.1515, University of Ilorin, Nigeria
2 Department of Chemistry, University of Uyo, Nigeria.
*corresponding author : jobaleye@yahoo.com; jobaleye@unilorin.edu.ng
Abstract
4-methoxyaniline-5,10,15,20-tetraphenylporphyrinatozinc(II),[(ZnTPP(MOAN)]1
was
synthesized (MOAN = 4-methoxyaniline) and characterised by elemental analysis and
spectroscopic techniques. The molecular structure of 1 was determined by single crystal X-ray
crystallography. The structure revealed a triclinic crystal system and the space group P1 with the
central metal adopting slightly distorted square pyramidal geometry with 4-methoxyaniline in
the axial position. The antimicrobial activities were carried out using well diffusion method and
the zone of inhibition of four bacteria and two fungi was measured.
Keywords : Porphyrin, 4-methoxyaniline, crystal structure, spectra, antimicrobial activity.
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Introduction
Porphyrin and chlorin derivatives are among the most important tetrapyrrolic macrocycle.
Synthetic porphyrins and metalloporphyrins have been applied in chemotherapy particularly in
cancer treatment by boron neutron capture therapy (BNCT) and photodynamic therapy (PDT)
[1,2]
. PDT technique is considered an alternative to cystostatics and radiotherapy. It is indeed
preferred because of its selectivity. Photosensitizers selectively localise themselves in the
[3,4]
affected cancerous tissue which cause death of tumour cells or damage the neoplastic tissue
.
Relationship exists between cancer and metals as acknowledged by recent developments in the
field of metal-based anticancer agents [5]
Porphyrins and their metal complexes function as photosensitizers in PDT. Their efficiency in
the technique is due to energy transfer from the porphyrin triplet state to the oxygen ground state.
They have high singlet oxygen quantum yields with apparent lack of toxicity. It has been
reported that a long-life triplet state is required for efficient photosensitization and incorporation
[6]
of diamagnetic metals such as zinc into the porphyrin macrocycles aids this process
.
Similarly, it was discovered that porphyrins bearing methoxy group on meso-phenyl group
enhance photophysical properties of a photosensitizer [7]. 4-Methoxyaniline readily forms Schiff
bases which coordinate metals to form complexes with various biological activities [8-11] . This
work focuses on preparing metalloporphyrins containing methoxy substituent and a diamagnetic
metal as potential photosensitizers in photodynamic therapy for cancer treatment. In order to
contribute further towards synthesis and structural determination of metal complexes with
[12,13]
application in chemotherapy
, we hereby report the synthesis of [ZnTPP(MOAN)]1
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complex containing 4-methoxyaniline ligand which is expected to contribute to the coordination
chemistry of porphyrin.
EXPERIMENTAL
Materials
Propionic acid, pyrrole, and benzaldehyde were purchased from Sigma-Aldrich. Pyrrole was
distilled on an oil bath immediately before use.Synthesis grade triethylamine was purchased
from Scharlau Chemie S.A. while chloroform and 4-methoxyaniline were from M&B
Laboratory. Dichloromethane was from Koch Light Laboratories and distilled over K2CO3
before use. Zinc chloride (ZnCl2) was obtained from British Drug House Chemical Limited,
Poole, England.
Physical measurements
Elemental analysis (C,H and N) was performed on Thermo Flash 1112 CHNSO elemental
analyser. Electronic spectra of the ligands and their complexes were recorded in dichloromethane
solution and on Jenway 6405 UV-Visible spectrophotometer in the range 200-1100 nm. The IR
spectra were recorded on Shimadzu 8400S FTIR spectrophotometer as KBr pellets in the range
1
4000-400cm-1. The H and 13C NMR spectra were recorded on NMR spectrometer, Mercury
Varian BB 200 using deuterated chloroform as solvent and tetramethylsilane (TMS) as the
internal standard.
Synthesis of 5, 10, 15, 20-Tetraphenylporphyrin (TPPH2).
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TPPH2 was synthesized from pyrrole and benzaldehyde using previously described method
[14,15]
Adler-Longo
(see Electronic supplementary Information,Scheme 1)
Synthesis of 5, 10, 15, 20-Tetraphenylporphyrinatozinc(II) (ZnTPP).
ZnTPP was synthesized using known method reported by Terazono, et al [16] and Sapien and
[17]
Grazynski
and some modifications were adopted for the synthesis (see Electronic
supplementary Information,Scheme 2)
Synthesis of 4-Methoxyaniline-5, 10, 15, 20-tetraphenylporphyrinatozinc (II)
(ZnTPP(MOAN)1.
4-Methoxyaniline (0.0688 g, 0.5386 mmol) dissolved in 12.5 ml of chloroform (yellowish-brown
solution) was slowly added to a reddish-pink solution of ZnTPP (0.0854 g, 0.126 mmol) in hot
chloroform (15 ml). The mixture was boiled under reflux for 1hr to obtain a purple solution after
which the stirring continued for 11 hours at room temperature. The resulting red-purple solution
was allowed to evaporate slowly. After 11 days a reddish-purple crystalline residue was
obtained. A bright red-purple solution of the residue in dichloromethane gave a single spot on
TLC plate. The crude product was recrystallized from toluene to give blue-purple single crystals
suitable for X-ray crystallographic studies.
Yield = 87.22% (0.1345 g). Melting point: 342 °C.801.281; Anal. Calcd. for ZnC51H37N5O (%):
C, 76.45; H, 4.65; N, 8.74. Found: C, 75.72; H, 4.86; N, 8.53. UV-vis (CH2Cl2): λmax (nm) 330,
350, 415, 425, 550, 584. IR (KBr, cm-1): 3371, 3308, 3104, 3024, 2832, 1595, 1483, 1512, 1439,
1389, 1339, 1298, 1242, 1204, 1067, 1040, 1001, 750, and 702.
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X-ray Crystallography of 1
A blue-purple crystal of [ZnTPP(MOAN)]1 was on a glass fiber and mounted on a crysloop
with Paratone-N oil and data collected using Bruker D8 Venture Dual Source diffractometer
equipped with a CMOS-detector using graphite-monochromated Mo Kα(γ = 0.71073Å) radiation
at 293K.
The structure of 1 was solved by direct methods using (SHELXS-86, Sheldrick, G.M., 1990) [19]
and completed by iterative cycles ΔF synthesis, using the ( SHELXL-97 packages ,Sheldrick,
[21]
G.M., 1997) [20]. . The structure was solved by Charge Flipping using SUPERFLIP
(Superflip, 2007) and refined by full-matrix least-squares methods based on F2 using SHELXL
(Sheldrick, G.M., 2008) [22] Details of the crystal parameters, data collection and refinements are
listed in Table 4. ). Molecular graphics or complete structure solution, refinement and analysis
[23]
program was achieved using OLEX2 (Dolomanor et al,
. Table 5 lists selected bond length
describing the zinc atom coordination with the porphyrin core and the 4-methoxyaniline ligand.
Antibacterial and antifungi susceptibility tests
The in vitro biological effects of the investigated compounds were tested against important
[24]
bacteria and fungi strains by well diffusion method
. Cloxacillin was used as reference drug
for bacteria. The drug, 4-methoxyaniline and the metal complex [ZnTPP(MOAN)] 1 were
screened in-vitro activity against one Gram-positive bacteria, Staphylococcus aureus, three
Gram-negative bacteria, Proteus vulgaris, Escherichia coli and Klebsiella pneumonia, and two
fungi species, Candida albican and Aspergillus niger. The media used for this test were nutrient
agar, nutrient broth and potato dextrose agar. Proteus vulgaris was obtained from University
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College Hospital, Ibadan, Nigeria. Staphylococcus aureus, Escherichia coli and Klebsiella
pneumonia were collected from University of Ilorin Teaching Hospital, Nigeria. The fungi were
obtained from the Microbiology Department University of Ilorin, Nigeria.
Solutions (0.2 ml) of each compound (16 mg) under test in 10 ml of dimethylsulphoxide
(DMSO) containing 320µg were pipetted into the bored media wells and allowed to disperse
evenly. The plates were then incubated for 24 hours at 37 °C in the case of bacteria and at room
temperature (about 28 °C) for 72 hours in the case of fungi. After incubation zones of clearance
were observed and diameter of these inhibition zones was measured.
RESULTS AND DISCUSSION
Formation and characterization of zinc (II) complex
Insertion of zinc into the ligand TPPH2 was achieved by dissolving ZnCl2 in methanol and
refluxing the resulting solution with a chloroform solution of the ligand. Four coordinate ZnTPP
was formed. The progress of the reaction was conveniently followed by electronic spectroscopy.
The second ligand MOAN was thereafter introduced to ZnTPP to obtain [ ZnTPP(MOAN)]1, a
five coordinate complex.
The percentage yield of the complex was excellent (above 80%) and greater than that of ZnTPP
from which it was prepared. This shows that MOAN readily react with the metalloporphyrin
and coordinate with metal ions. In fact, 4-methoxyaniline and its structural isomers form many
[10,11]
Schiff bases and their metal complexes
The use of the chloroform as solvent for both
.
metalloporphyrin and the organic compound during the synthesis might have also enhanced the
metallation process as suggested by Adler et al [25]. C, H, N analysis shows a good agreement
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with the theoretical percentage of each of the elements. The coordination number of zinc
increased to five as suggested by the analytical results.
UV-Visible Spectra
Table 1 shows the results of UV-vis spectral data and their assignments. The effect of axial
ligation on the electronic absorption spectral properties of ZnTPP was also investigated. The
bands observed in the spectra of [ZnTPP(MOAN)] 1 was as a result of π to π* electronic
transitions in the porphyrin and 4-methoxyaniline ring systems. The two organic molecules
(MOAN and TPPH2) contain highly conjugated π electrons which masked any d-d transition in
the metal ion orbitals. Unlike most transition metal complexes, the colour of metalloporphyrins
are attributed to absorption within the porphyrin ligand involving excitation of electrons from π
to π* of porphyrin ring orbital. This can be explained by considering the four frontier orbitals
(HOMO and LUMO orbitals). According to Gouterman’s four-orbital model[26] , the transition
a1u(π) → eg(π*) and a2u(π) → eg(π*) are largely responsible for the Soret and Q (α and β) bands
of metalloporphyrins. The dxz and dyz (dπ) orbitals of normal metalloporphyrins (d0 or d10) are
of relatively low energy and have very little effect on the porphyrin π → π* energy gap in
[27]
porphyrin
. The peaks observed in the mixed ligand complexes were quite different from
those of metalloporphyrin reactants. These peaks experienced blue shifts and two new peaks at
482 and 510 nm were observed as Q bands in the zinc complex. Small bathochromic shifts have
been reported to characterise the addition of oxygen donor axial ligands to ZnTPP by Narda and
[28]
Dawson
. The hypsochromic shift suggested that MOAN was not an oxygen donor but a
nitrogen donor toward the metal in ZnTPP. The spectral changes can be attributed to the
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coordination of metal ions by MOAN so as to form more stable geometry by expanding their
coordination spheres. B bands or Soret peaks however did not experience any appreciable shift.
Square-pyramidal geometry was reported to be common to pentacoordinate zinc (II) porphyrins
[16]
.
Infrared spectrum of [ZnTPP(MOAN])1
Table 2 displays the spectral bands of [ZnTPP(MOAN)]1 compared with those of the
metalloporphyrin ZnTPP on one hand and those of TPPH2 and MOAN on the other. Stretching
and deformation bands of C-H of methoxy group were present in the mixed ligand complexes
and in the spectrum of MOAN as expected which indicate the presence of p-anisidine in them.
Similarly, C-Ostr frequency bands appeared in the complexes which did not undergo significant
shift compared to the bands in MOAN. This suggests that methoxy group of MOAN was not
involved in the coordination with the metal ion. In the spectra of ZnTPP(MOAN), N-Hstr and C-
Nstr bands were present and shifted to lower frequencies when compared to the same band in
MOAN. This shift can be attributed to the utilization of N-H group for coordination. The metal-
nitrogen [29] stretching bands around 1000 cm-1 were found present in the mixed ligand complex
but experienced red shift from the band of ZnTPP as a result of coordination with MOAN
through the nitrogen atom. It had been reported that ZnTPP usually take up only one axial ligand
resulting in five-coordinated zinc atom [28,30] and peripheral phenyl groups in the complex do not
[31]
create any steric hindrance to coordination of bases
. The finding in this work further
confirmed the above report by previous workers. The addition of molar excess of MOAN to
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ZnTPP (4:1 mole ratio) only produced a complex of 1:1 stoichiometry as revealed by analytical
and spectroscopic results.
Crystal and molecular structure of [ZnTPP(MOAN)]1
The structure of the compound has been studied by X-ray diffraction. Crystallographic
parameters and refinement results for 1 are shown in Table 3.Three views of the complex are
shown in Figure S1 . selected bond lengths and angles are presented in Tables 4 and 5
respectively. The zinc is five-coordinate zinc (II) porphyrin. The Zn-Nporphyrin distance (average
2.0596 Å) is comparable with the distance found for similar bonds in five-coordinate zinc-
[33, 34,35]
porphyrin complexes (Zn-N = 2.057(1)-2.076(9)Å)
(Table 4) but are longer than Zn-N
distance (2.036 Å) in four coordinate ZnTPP [36]. Thus, the complex possesses a moderately
expanded porphyrin core (2.052 Å). The equatorial Zn-Nporphyrin bond distance is smaller than
axial Zn-N5 bond distance (2.2053 Å). The 4-methoxyaniline molecule is weakly bound to the
zinc atom by comparison with the much shorter Zn-Npyridyl bond distance of 2.140(8) Å estimated
[37]
in the pyridine adduct of [5, 10, 15, 20-tetrakis(heptafluoropropyl)porphinato]zinc (II)
. The
Zn-Npyrrolic bond distances (2.0556-2.0665 Å) are, however, within the range of that reported for
similar complexes (2.052-2.076 Å) [38]
.
The four Zn-N bonds (Zn-N1 to Zn-N4) are non-equivalent as shown in Table 4. This could be
caused by in-plane elongation of the porphyrin core due to steric strain enforced by the
peripheral substituents. The mechanism of the core is explained by repulsion of the pyrrolic β-β
substituents that push the meso-phenyl groups towards the unsubstituted pyrroles [39]
.
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The primary amino group did not become deprotonated on coordination as suggested by the
results of infrared spectroscopy. It implies that a lone pair of electron on the nitrogen atom was
utilized for coordination with zinc metal. The crystal structure is shown in figure 1.
Antibacterial and antifungal tests
Cloxacillin was used as reference drug for bacteria. The inhibition zones developed at the
concentration of 1600μg/L (1.6mg/ml) in DMSO are shown in Table 8. The complex formed by
ZnTPP with MOAN inactivates the organic compound 4-methoxyaniline against E. coli. The
presence of the metalloporphyrin which is not well known to be biologically active compared to
the reported activities of metal complexes of MOAN. [ZnTPP(MOAN)]1 displayed no activity
against all other bacteria species tested. Compound 1 is comparable in activity with 4-
methoxyaniline against Candida albican fungi at the concentration used. This activity may have
been imparted on the complex by the axial ligand. This is not unexpected since porphyrins and
metalloporphyrins were not reported as having significant antimicrobial activity. They were,
however, found to act as photosensitizers in photodynamic therapy.
Conclusion
In summary, we reported the first Zinc-porphyrin complex containing 4-methoxyaniline.
Spectroscopic and X-ray crystal studies of [ZnTPP(MOAN)] revealed that the complex contains
4-methoxyaniline in the axial position and coordinate the central metal through the nitrogen atom
without loss of hydrogen atoms of the primary aromatic amine while leaving methoxy group
unbound. The Zn-Nporphyrin distance is comparable with the distance found for similar bonds in
five-coordinate zinc-porphyrin complexes. Antimicrobial investigations of the compound
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indicate that it is moderately effective against Candida albican but showed no activity against
the four bacteria selected for the test. The presence of methoxy group and the diamagnetic zinc
may make the new compound a better photosensitizer in photodynamic therapy for the treatment
of cancer.
Supplementary Material.
Supplemental data is available at the publisher’s website. CCDC 968549 contains the
supplementary crystallographic data for this paper. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html(or from the Cambridge crystallographic Data
Centre , 12, Union Road, Cambridge CB2 1EZ; fax +441223336033). Electronic supplementary
Information ESI available.
Acknowledgement
We are grateful for the support from the World Bank Science and Technology Education Post-
Basic Project (STEP-B), Department of Chemistry University of Ilorin, Nigeria and Markus
Neuburger for help with the crystal structure determination during the Zurich School of
Crystallography 2012 at the University of Zurich, Institute of Organic Chemistry,
Winterthurersthrasse 190 CH-8057, Zurich. We thank Prof. Mino Caira of the University of
Cape Town, South Africa for supplying the various views of ZnTPP(MOAN)
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References
1.
2.
McCaughan J.S. Jr: Photodynamic Therapy. A review. Drugs Aging 1999, 15, 49 – 68.
Guenter G., Andrea L., Klaus B., Matthias Z., Clemens F., and Schuerer N.Y.: Porphyrin
concentrations in various human tissues. Experimental Dermatology 1995, 4(4, pt. 1),
218-220.
3.
4.
Dougherty T.I. : Photodynamic therapy. Photochem. Photobiol. 1993, 58, 895-900.
Penning L.C. and Dubbelman, T.M.: Fundamentals of photodynamic therapy: cellular
and biochemical aspects. Anticancer Drugs 1994, 5, 139 – 146.
5.
6.
7.
Wang X.: Fresh platinum complexes with promising antitumor activity. Anti-cancer
Agents in Medicinal Chemistry 2010, 10, 396-411.
Rodica-Mariana I.O.N.: Photodynamic therapy(PDT): A photochemical concept with
medical applications. Revue Roumaine de Chimie, 2007, 52(12), 1093-1102.
Katona Z., Grofcsik A., Baranyai P., Bitter I., Grabner G., Kubinyi M. and Vidoczy T. :
Triplet state spectroscopic studies on some 5,10,15,20–tetrakis(methoxyphenyl)
porphyrins. J. Mol. Structure 1998, 450, 41-45.
8.
Elzahany E.A., Hegab K.H., Khalil S.K.H., and Youssef N.S.: Synthesis, characterization
and biological activity of some transition metal complexes with Schiff bases derived from
2-formylindole, salicylaldehyde, and N-amino rhodanine. Australian Journal of Basic
and Applied Sciences 2008, 2(2), 210-220.
12
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
9.
Roman N.: Antifungal active tetraazamacrocyclic transition metal complexes: Designing,
template synthesis, and spectral characterization. Russian Journal of Coordination
Chemistry 2009, 35(3), 234-238.
10.
Mishra A.P. and Gupta P.: Effect of chelation on therapeutic potential of drugs:
Synthesis, structure, antimicrobial and insecticidal activity of 3d-metal complexes
involving Schiff-bases. Journal of Chemical and Pharmaceutical Research 2011, 3(2),
150-161.
11.
12.
13.
14.
Panchal P.K., Parekh H.M., Pansuriya P.B., and Patel M.N.: Bactericidal activity of
different oxovanadium(IV) complexes with Schiff bases and application of chelation
theory. Journal of Enzyme Inhibition and Medicinal Chemistry 2006, 21(2), 203-209.
Obaleye J.A., Caira M.R. and Tella A.C.: Synthesis, characterization and crystal structure
of a polymeric zinc(II) complex containing the antimalarial Quinine as ligand. J. Chem.
Crystallography 2007, 37(10), 707-712.
Obaleye J.A., Caira M.R. and Tella A.C.: Synthesis, characterization and crystal
structures of the tetrachlorocuprate and tetrabromocadmate salts of the antimalarial
mefloquine. Structural Chemistry 2009, 20, 859-868.
Adler A.D., Longo F.R., and Shergalis W.: Mechanistic investigations of porphyrin
syntheses. 1. Preliminary studies on ms-tetraphenyl-porphin. Journal of American
Chemical Society 1964, 86, 3145-3149.
13
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
15.
16.
17.
18.
Adler A.D., Longo F.R., Finarelli J.D., Goldmacher J., Assour J., and Korsakoff L.: A
simplified synthesis for meso-tetraphenylporphyrin. Journal of Organic Chemistry 1967,
32, 476.
Terazono Y., Patrick B.O. and Dolphin D.H.: Synthesis, crystal structures and redox
potentials
of
2,3,12,13-tetrasubstituted-5,10,15,20-tetraphenylporphyrinzinc(II)
complexes. Inorganic Chemistry 2002, 41(25), 6703-6709.
Stepien M. and Latos-Grazynski L.: Core-modified porphyrin incorporating a phenolate
donor. Characterization of Pd(II), Ni(II), Zn(II), Cd(II), and Fe(III) complexes. Inorganic
Chemistry 2003, 42, 6183-6193.
Woller E.K. and DiMagno S.G.: 2, 3, 7, 8, 12, 13, 17, 18-Octafluoro-5, 10, 15, 20-
tetraarylporphyrins and their zinc complexes: First spectroscopic, electrochemical, and
structural characterization of a perfluorinated tetraarylmetalloporphyrin. Journal of
Organic Chemistry 1997, 62, 1588-1593.
19.
20.
21
Sheldrick, G.M.: Phase annealing in SHELX-90 Direct method for layer structures. Acta
Crystallography, 1990, A 46, 467.
Sheldrick, G.M. Site LXL-97: Programme for crystal structure refinement; University of
Gottingen, 1997.
Palatinus L. and Chapurs G.: Superflip- a computer program for the solution of crystal
structures by charge flipping in arbitrary dimensions. J. Appl. Cryst. 2007, 40, 786
22
Sheldrick G.M.: A short history of SHELX. Acta Cryst. 2008, A64, 112
14
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
23
Dolomanov O.V., Bourhus L.J., Gildea R.J., Howard J.A.K. and Puschmann H.: OLEX2:
a complete structure solution, refinement and analysis program. Appl. Cryst. 2009, 42,
339.
24.
Thrupp L.D.: Susceptibility Testing of Antibiotic in Liquid Media, Antibiotics in
Laboratory Medicine, 2nd Edition, Victor Lorian, Williams and Williams, Balitimore,
1986, p.93-150.
25.
26.
Adler A.D., Longo F.R., Kampas F., and Kim J.: On the preparation of
metalloporphyrins. Journal of Inorganic and Nuclear Chemistry 1970, 32, 2443-2445.
Nappa M. and Valentine J.S.: The influence of axial ligands on metallo-porphyrins
visible absorption spectra. Complexes of tetraphenylporphinatozinc. Journal of the
American Chemical Society 1978, 100, 5075-5080.
27.
28.
29.
Suslick K.S. and Watson R.A.: The photochemistry of chromium, manganese, and iron
porphyrin complexes. New Journal of Chemistry 1992, 16, 633-642.
Nardo J.V. and DawsonJ.H.. Spectroscopic evidence for the coordination of oxygen
donor ligands to tetraphenylporphinatozinc”. Inorganica Chimica Acta 123, 9-13.
Prendergast K. and Spiro T.G.: Core expansion, ruffling and doming effects on
metalloporphyrins vibrational frequencies. Journal of American Chemical Society 1992,
114, 3793-3801.
15
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
30.
Redkevich D.M., Verboom W. and Reinhoudt D.N.: Capped biscalix [4] arene-Zn-
porphyrin: Metalloreceptor with a rigid cavity. Journal of Organic Chemistry 1995,
60(20), 6585-6587.
31.
Lebedeva N.S., Pavlycheva N.A., and V’yugin A.I.: Basicity parameter of weak organic
bases derived from thermodynamic parameters of their reactions with
(tetraphenylporphyrinato)zinc(II). Russian Journal of Organic Chemistry 2004, 40(12),
1727-1736.
32.
Smith N.W. and Dzyuba S.V.: Efficient nitration of meso-tetraphenyl-porphyrin with
nitronium tetrafluoroborate. ARKIVOC 2010, (iii), 10-18.
33. Cullen D.L. and Meyer E.F. Jr.: The crystal
and molecular structure of
2,3,7,8,12,13,17,18-octaethylporphinatomonopyridinezinc(II). Acta Crystallogr., Sect. B;
Struct. Crystallogr. Cryst. Chem. 1976, B32, 2259.
34. Collins D.M. and Hoard J.L.: Crystal structure and molecular stereochemistry of alpha,
beta, gamma, delta- tetra(-4-pyridyl)porphinatomonopyridinezinc(II). Appraisal of bond
strain in the porphine skeleton. J. Am. Chem. Soc. 1970, 92, 3761.
35. Spaulding L.D., Eller P.G., Bertrand J.A., and Felton R.H.: Crystal and molecular
structure of the radical perchloratotetraphenylporphinatozinc(II). J. Am. Chem. Soc. 1974,
96, 982.
36. Scheidt W.R., Kastner M.E. and Hatano K. Inorg. Chem. 1978,17, 706.
16
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37. Goll J.G., Moore K.T., Ghosh A., and Therien M.J.: Synthesis, structure, electronic
spectroscopy, photophysics, electrochemistry, and X-ray photoelectron spectroscopy of
highly-electron-deficient
[5,10,15,20-tetrakis(perfluoroalkyl)porphinato]zinc(II)
complexes and their free base derivatives. J. Am. Chem. Soc. 1996, 118, 8344- 8354.
38. Jameson G.B., Molinaro F.S., Ibers J.A., Collman J.P., Brauman J.I., Rose E., and
Suslick K.S.: J. Am. Chem. Soc. 1978, 100, 6769-6770.
39.
Sanders J.K.M., Bampos N., Clyde-Watson Z., Darling H.J.C., Kim H.J., Mak C.C., and
Webb S.J.: In The Porphyrin Handbook, Kadish K.M., Smith K.M., and Guilard R.(eds),
Academic Press; San Diego C.A. (2000),.vol.3, pp.1-48.
40. Schauer C.K., Anderson O.P., Eaton S.S., and Eaton G.R.: Crystal and molecular
structure of a six-coordinate zinc porphyrin: bis(tetrahydrofuran)(5,10,15, 20-
tetraphenylporphinato)zinc (II). Inorg. Chem. 1985, 24, 4082-4086.
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Table 1. Electronic absorption bands of TPPH2 and its Zinc complexes
Compound
Visible absorption bands (nm)
Assignment
B band
(Soret)
Q bands
TPPH2
415
425
429
435
515, 550, 590, 650
545, 585
π → π*
π → π*
π → π*
π → π*
ZnTPP
[ZnTPP(MOAN)] 1
MOAN
482, 510, 541, 584
360, 405
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Table 2. Infrared spectra results of 5, 10, 15, 20-Tetraphenylporphyrin and its metal complexes
IR Band Assignment
(KBr,cm-1)
TPPH2
ZnTPP
3435w
1338m
995s
MOAN
ZnTPP(MOAN)
3371m
N-Hstr (arom. amine)
C-Nstr (arom. amine)
M-Nstr
3317m
3424s,
3349m
1350s
1333w
1339s, 1298w
1001s
-
-
-
C-Ostr
-
1275m,
1242m, 1204w,
1234s, 1032s 1067s, 1040m
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Table 3 . Crystallographic parameters and refinement results for 1
molecular formula
molecular weight:
space group
temperature (K):
colour:
C51H37N5OZn
801.23
P1
293
Purple-blue
Triclinic
crystal system
unit cell dimensions:
a (Å)
10.580(5)
10.702(5)
18.305(5)
79.492(5)
86.445(5)
78.066(5)
1993.2(14)
2
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
Z
Dcalc (Mgm-3)
µ (mm-1)
F(000)
1.335
0.66
832
Radiation
Mo Kα(λ = 0.71073 Å)
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θ range
2.1-27.5°
h, l, k collected
± 13, ±13, ±23 (fine-focus sealed tube graphite)
reflections with I > 2σ(I)
no of reflections collected
no of independent reflections
Rw (F2)
7515
44978
9107 [Rint = 0.055]
0.120
slope of normal prob plot
Largest diff. peak/hole/e Å-3
1.13
0.39/-1.01
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Table 4 . Bond Lengths (Å) Describing the Zinc Atom Coordination, the Porphyrin Core, and
the MOAN Ligand
Zn1-N1
Zn1-N2
Zn1-N3
Zn1-N4
Zn1-N5
N3-C5
2.0567 (18)
2.0556 (18)
2.0597 (18)
2.0665 (18)
2.2053 (18)
1.374 (3)
1.378 (3)
1.376 (3)
1.377 (3)
1.432 (3)
1.372 (3)
1.377 (3)
1.374 (3)
1.376 (3)
N3-C8
N2-C13
N2-C10
N5-C45
N4-C20
N4-C3
N1-C15
N1-C18
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Table 5 . Bond Angles (deg) Describing the Zinc Atom Coordination, the Porphyrin Core,
and the MOAN Ligand
N2-Zn1-N1
N2-Zn1-N3
N1-Zn1-N3
N2-Zn1-N4
N1-Zn1-N4
N3-Zn1-N4
N2-Zn1-N5
N3-C5-C4
N3-C5-C6
N1-Zn1-N5
N3-Zn1-N5
N4-Zn1-N5
89.31 (7)
89.55 (7)
166.81 (7)
167.34 (7)
89.08 (7)
89.16 (7)
97.34 (7)
125.66 (18)
109.42 (17)
98.24 (7)
94.93 (7)
95.32 (7)
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C5-N3-C8
106.62 (17)
126.49 (13)
126.45 (14)
126.60 (14)
126.09 (14)
114.67 (13)
126.70 (14)
125.69 (13)
125.77 (18)
109.44 (17)
125.63 (18)
109.17 (18)
125.30 (18)
106.76 (16)
126.10 (13)
126 58 (14)
C5-N3-Zn1
C8-N3-Zn1
C13-N2-Zn1
C10-N2-Zn1
C45-N5-Zn1
C20-N4-Zn1
C3-N4-Zn1
N4-C3-C4
N4-C3-C2
N1-C18-C19
N1-C18-C17
N4-C20-C19
C15-N1-C18
C15-N1-Zn1
C18-N1-Zn1
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N1-C15-C14
N1-C15-C16
N4-C20-C1
N2-C13-C14
N2-C13-C12
N3-C8-C9
126.01 (19)
109.51 (18)
109.58 (17)
125.47 (18)
109.39 (18)
125.18 (19)
109.58 (18)
125.80 (19)
109.21 (18)
N3-C8-C7
N2-C10-C9
N2-C10-C11
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Table 6 . Comparative Structural Analysis of Zinc Porphyrins [40]
zinc-porphyrin complex
(Zn-N)av (Å)
2.0596(18)
2.076 (9)
2.036 (6)
2.067 (6)
2.073 (8)
2.057 (1)
Ref
ZnTPP(ANSD)
this work
ZnTPP(ClO4)
ZnTPP.2C6H5CH3
ZnOEP(py)
32
33
34
35
39
Zn(TPyP)(py)
ZnTPP(THF)2
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Table 7. Zones of inhibition of bacteria and fungi by Cloxacillin and ZnTPP(MOAN) at
1.6mg/ml (DMSO)
Organism/
Staphylococ Klebsiella
Escherichia Proteus
Candida Aspergillus
albican niger
Compounds
cus aureus
pneumoniae coli vulgaris
Zones of Inhibition (mm)
Cloxacillin
MOAN
15
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
Inactive
17
15
15
Inactive
Inactive
Inactive
Inactive
30
[ZnTPP(MOAN Inactive
)]
Inactive
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Scheme 3. Synthesis of [ZnTPP(MOAN)] 1
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Figure 1. Thermal ellipsoid plot of ZnTPP(MOAN)1
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