Some oxovanadium(IV) complexes of SA/SSA and 5, 10, 15, and 20-meso-tetraphenylporphyrin (H2tpp) with unidentate and bidentate nitrogen donors have been synthesized and characterized by elemental analysis, conductivity measurements, magnetic susceptibility, UV-Vis, IR, mass spectroscopy, TGA/DTA, and 1H, 13C and 51V NMR studies to investigate the steric and electronic effects of axial ligands on the properties of porphyrins. On the basis of these studies, it has been investigated that the axial ligands bind to the sixth coordination site of the vanadium ion to form a relatively stable six-coordinate-porphyrin complex where as in the case of SA/SSA complexes the nitrogen donors bind to the equatorial position giving square pyramidal geometry. The in vitro cytotoxicity against human cancer cell lines and antimicrobial activities of the synthesized compounds have been done against various fungal and bacterial pathogens. The [VO(SA/SSA)L/L-L] complexes were found to possess higher antibacterial, antifungal activity and in vitro cytotoxicity against human cancer cell lines than VO(tpp)L complexes. 1. Introduction Macrocyclic nitrogen donor ligands [1] have received special attention because of their versatile coordination modes [2] and for their biological activities, that is, toxicity against bacterial [3] and fungal growth, anticancerous [4], and other biochemical properties [5]. Such ligands, for example, porphyrins, salicylates, and sulphosalicylates, are known to play a very important and vital role in the stability of the metal complexes with the factor of having specific cavity size, stereochemical rigidity, flexibility, and ability to coordinate with metal atom [6]. SA/SSA ligands and their complexes are widespread in nature and of considerable relevance in medicinal chemistry [7] and also in industries [8, 9] (e.g., in the preparation of heterometallic precursors to oxide materials). VO2+ complexes have extensive clinical applications. However, there have been no reports on the corresponding organo oxovanadium(IV) salicylates, sulphosalicylates and porphyrins, though these compounds are expected to be biomedically relevant [10, 11]. We report herein the synthesis of some mixed ligand complexes (containing different donor atoms) and characterisation by means of spectral and magnetic studies as well as in vitro biological assays of some of the complexes. Structural correlation of these complexes has also been made and a square pyramidal geometry around [VO(SA/SSA)L/L-L] and an octahedral geometry around [VO(tpp)L] complexes are proposed on the basis
References
[1]
R. Sellappan, S. Prasad, P. Jayaseelan, and R. Rajavel, “Synthesis, spectral characterization, electrochemical and antimicrobial activity of macrocyclic schiff base vanadyl complexes,” Rasayan Journal of Chemistry, vol. 3, no. 3, pp. 556–562, 2010.
[2]
P. Sengupta, R. Dinda, S. Ghosh, and W. S. Sheldrick, “Synthesis and characterization of some biologically active ruthenium(II) complexes of thiosemicarbazones of pyridine 2-aldehyde and thiophene 2-aldehyde involving some ring substituted 4-phenylthiosemicarbazides and 4-Cyclohexylthiosemicarbazide. Crystal Structure of Cis-[Ru(Pph3)2(L6H)2](Clo4)2?2H2O [L6H=4-(Cyclohexyl) Thiosemicarbazone of Pyridine 2-Aldehyde],” Polyhedron, vol. 22, no. 3, pp. 447–453, 2003.
[3]
M. A. Pujar, B. S. Hadimani, S. Meenakumari, S. M. Gaddad, and Y. F. Neelgund, “Azo and schiff bases and their metal complexes as antibacterial compounds,” Current Science, vol. 55, no. 7, pp. 353–354, 1986.
[4]
L. Mishra, A. Jha, and A. K. Yadaw, “Synthesis, spectroscopic and antifungal studies of transition metal trinuclear/polynuclear complexes with azolo-2,4-pentane-dione: part III,” Transition Metal Chemistry, vol. 22, no. 4, pp. 406–410, 1997.
[5]
L. J. Mishra, “Chelation and ungitoxicity,” Indian Chemical Society, vol. 76, no. 4, pp. 175–181, 1999.
[6]
M. Formica, V. Fusi, M. Micheloni, R. Pontellini, and P. Romani, “Cryptand ligands for selective lithium coordination,” Coordination Chemistry Reviews, vol. 184, no. 1, pp. 347–363, 1999.
[7]
V. Stavila, J. C. Fettinger, and K. H. Whitmire, “Synthesis and characterization of new phenylbis(salicylato)bismuth(III) complexes,” Organometallics, vol. 26, no. 14, pp. 3321–3328, 2007.
[8]
R. M. Smith, A. E. Martell, and R. S. Motekaitis, NIST Critically Selected Stability Constants of Metal Complexes Database, Version 4.0, Texas A and M University, College Station, Tex, USA, 1997.
[9]
A. E. Martell, R. J. Motekaitis, and R. M. Smith, “Aluminium complexes of hydroxyaliphatic and hydroxyaromatic ligands in aqueous systems-some problems and solutions,” Polyhedron, vol. 9, no. 2-3, pp. 171–187, 1990.
[10]
T. K. Saha, Y. Yoshikawa, H. Yasui, and H. Sakurai, “Oxovanadium(IV)-porphyrin complex as a potent insulin-mimetic. Treatment of experimental type 1 diabetic mice by the complex [meso-tetrakis(4-sulfonatophenyl)porphyrinato]oxovanadate(IV)(4-),” Bulletin of the Chemical Society of Japan, vol. 79, no. 8, pp. 1191–1200, 2006.
[11]
H. Sakurai, T. Inohara, Y. Adachi, K. Kawabe, H. Yasui, and J. Takada, “A new candidate for insulinomimetic vanadium complex: synergism of oxovanadium(IV)porphyrin and sodium ascorbate,” Bioorganic and Medicinal Chemistry Letters, vol. 14, no. 5, pp. 1093–1096, 2004.
[12]
A. D. Longo, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour, and L. Korsakoff, “A Simplified Synthesis for meso-tetraphenylporphine,” The Journal of Organic Chemistry, vol. 32, no. 2, pp. 476–476, 1967.
[13]
A. R. Menotti, “Porphyrin studies. IV. 1 The Synthesis of α,β,γ,δ-Tetraphenylporphine,” Journal of the American Chemical Society, vol. 63, no. 1, pp. 267–270, 1941.
[14]
J. M. Vincent, “Distortion of fungal hyphae in the presence of certain inhibitors,” Nature, vol. 159, p. 850, 1927.
[15]
F. Oke, B. Aslim, S. Ozturk, and S. Altundag, “Essential oil composition, antimicrobial and antioxidant activities of Satureja cuneifolia Ten,” Food Chemistry, vol. 112, no. 4, pp. 874–879, 2009.
[16]
A. Thiantanawat, B. J. Long, and A. M. Brodie, “Signaling pathways of apoptosis activated by aromatase inhibitors and antiestrogens,” Cancer Research, vol. 63, no. 22, pp. 8037–8050, 2003.
[17]
X. Tong, S. Lin, M. Fujii, and D. X. Hou, “Echinocystic acid induces apoptosis in HL-60 cells through mitochondria-mediated death pathway,” Cancer Letters, vol. 212, no. 1, pp. 21–32, 2004.
[18]
S. Singh, D. P. Rao, A. K. Yadava, and H. S. Yadava, “Synthesis and characterisation of oxovanadium (IV) complexes with tetradentate schiff base ligands having thenil as precursor molecule,” Current Research in Chemistry, vol. 3, no. 2, pp. 106–113, 2011.
[19]
R. Murugavel and R. Korah, “Structural diversity and supramolecular aggregation in calcium, strontium, and barium salicylates incorporating 1,10-phenanthroline and 4,4′-bipyridine: probing the softer side of group 2 metal ions with pyridinic ligands,” Inorganic Chemistry, vol. 46, no. 26, pp. 11048–11062, 2007.
[20]
E. Akalin and S. Akyuz, “The FT-IR spectroscopic investigation of transition metal(II) 4-aminopyridine tetracyanonickelate complexes,” Journal of Molecular Structure, vol. 482, pp. 171–174, 1999.
[21]
V. K. Monga, K. H. Thompson, V. G. Yuen et al., “Vanadium complexes with mixed O,S anionic ligands derived from maltol: synthesis, characterization, and biological studies,” Inorganic Chemistry, vol. 44, no. 8, pp. 2678–2688, 2005.
[22]
Z.-C. Sun, Y.-B. She, Y. Zhou, X.-F. Song, and K. Li, “Synthesis, characterization and spectral properties of substituted tetraphenylporphyrin iron chloride complexes,” Molecules, vol. 16, no. 4, pp. 2960–2970, 2011.
[23]
E. J. Baran, A. H. Jubert, and E. G. Ferrer, “Infrared, raman and pre-resonance raman spectra of vanadyl(1V) tetraphenylporphyrin,” Journal of Raman Spectroscopy, vol. 23, pp. 489–494, 1992.
[24]
N. Dharmaraj, P. Viswanathamurthi, and K. Natarajan, “Ruthenium(II) complexes containing bidentate Schiff bases and their antifungal activity,” Transition Metal Chemistry, vol. 26, no. 1-2, pp. 105–109, 2001.
[25]
C. Zhuang, X. Tang, D. Wang et al., “An unsymmetrical porphyrin and its metal complexes: synthesis, spectroscopy, thermal analysis and liquid crystal properties,” Journal of the Serbian Chemical Society, vol. 74, no. 10, pp. 1097–1104, 2009.
[26]
L. Mishra and V. K. Singh, “Synthesis, structural and antifungal studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with new schiff bases bearing benzimidazoles,” Indian Journal of Chemistry, vol. 32, no. 5, pp. 446–457, 1993.