Acta Scientific Pharmaceutical Sciences (ASPS)(ISSN: 2581-5423)

Research Article Volume 4 Issue 8

Tetraazamacrocyclic Ligands and their Zinc(II) Complexes: Synthesis, Characterization and Biological Activities

Saswata Rabi1, Sabina Yasmin2, Foni Bushon Biswas2, Rahul Das2, Debashis Palit2 and Tapashi Ghosh Roy1*

1Department of Chemistry, Chittagong University of Engineering and Technology, Bangladesh
2Department of Chemistry, University of Chittagong, Bangladesh

*Corresponding Author: Tapashi Ghosh Roy, Department of Chemistry, Chittagong University of Engineering and Technology, Bangladesh.

Received: June 27, 2020; Published: July 23, 2020



The hexamethyl tetraazamacrocyclic ligand salt, Me6[14]diene. 2HClO4(L.2HClO4) has been synthesized by the condensation of ethylenediamine and acetone in the presence of HClO4, then two isomeric ligands tet-a and tet-b have been isolated from its reduced form. These ligands produced bimetallic and monometallic nitratozinc(II) complexes with Zn(NO3)2.6H2O. The nitratozinc(II) complexes, [(ZnL)2(NO3)](ClO4)3, [Zn(tet-a)(NO3)2] and [Zn(tet-b)(NO3)2] underwent axial addition and substitution reactions with KX (X= SCN, NO2, I or Br) in proper ratio to produce twelve new corresponding monometallic six coordinated octahedral complexes. The newly prepared complexes have been characterized on the basis of elemental analyses, IR, UV-Vis, and 1H-NMR spectroscopic, magnetic and molar conductivity data. Antibacterial activities of the ligands and complexes against different gram positive and gram negative bacteria have been investigated.

Keywords: Macrocyclic Ligands; Zinc(II) Complexes; Axial Addition and Substitution; Spectroscopic Studies; Antibacterial Activities



  1. Fabbrizzi, L., et al. “A microcalorimetric determination of the enthalpies of formation in solution of nickel(II) complexes with tetraazamacrocyclic ligands of varying size”. Inorganic Chemistry2 (1980):535-538.
  2. Singh D., et al. “Template synthesis and characterization of biologically active transition metal complexes comparing 14-membered tetraazamacrocyclic ligand”. Journal of Serbian Chemical Society2 (2010):217-228.
  3. Yao J., et al. “Synthesis, crystal structures and photoluminescent properties of the complexes of a new coumarin derivative with lanthanide ions”.Inorganic Chemistry Communication5 (2009):430-432.
  4. Suh MP., et al. “A redox-active two-dimensional coordination polymer: preparation of silver and gold nanoparticles and crystal dynamics on guest removal”. Journal of American Chemical Society14 (2006):4710-4718.
  5. Lippert B. “Cisplatin-chemistry and biochemistry of a leading anticancer drug”. WILEY-VCH<Weinheim (1999).
  6. Hermann P., et al. “Gadolinium(III) complexes as MRI contrast agents: ligand design and properties of the complexes”.Dalton Transaction 23 (2008):3027-3047.
  7. Ren YW., et al.“Carboxy ester hydrolysis promoted by two new bimetallic macrocyclic complexes. Synthesis, characterization and catalytic activity”. Transition Metal Chemistry5 (2006):611-615.
  8. Shankarwar SG., et al. “Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N4] macrocyclic ligand”. Spectrochimca Acta Part A, 145 (2015): 188-193.
  9. Pawar V., et al. “Synthesis, antioxidant and biocidal features of macrocyclic schiff bases with oxoanadium(V) complexes”. Journal of Chemical and Pharmaceutical Research1 (2011): 169-175.
  10. Illan-Cabeza NA., et al. “Synthesis, characterization and antiproliferative activity of metal complexes with the Schiff base derived from the condensation 1:2 of 2,6-diformyl-4-methylphenol and 5,6-diamino-1,3-dimethyluracil”. Journal of Inorganic Biochemistry4 (2008):647-655.
  11. Vanco J., et al. “Synthesis, structural characterization, antiradical and antidiabetic activities of copper(II) and zinc(II) Schiff base complexes derived from salicylaldehyde and β-alanine”. Journal of Inorganic Biochemistry4 (2008):595-605.
  12. Galal SA., et al. “New transition metal ion complexes with benzimidazole-5-carboxylic acid hydrazides with antitumor activity”. European Journal of Medicinal Chemistry4 (2009): 1500-1508.
  13. Chaviara AT., et al. “Copper(II) Schiff base coordination compounds of dien with heterocyclic aldehydes and 2-amino-5-methyl-thiazole: synthesis, characterization, antiproliferative and antibacterial studies. Crystal structure of CudienOOCl2. Journal of Inorganic Biochemistry8 (2004):1271-1283.
  14. Shakir M., et al. “Synthesis, spectroscopic characterization, and invitro antimicrobial screening of 16-membered tetraazamacrocyclic Schiff-base ligand and its complexes with Co(II), Ni(II), Cu(II), and Zn(II) ions”. Synthesis and Reactivity in inorganic Metal organic and Nano-metal Chemistry41 (2011):979-986.
  15. Yusoff SMA., et al. “Synthesis, characterization, and antibacterial activity of Cu(II), Ni(II) and Zn(II) complexes of 14-membered macrocyclictetraaza ligand”. Oriental Journal of Chemistry3 (2015):1751-1758.
  16. Benelli C., et al. “Electronic and CD spectra of catecholate and semiquinonate adducts of zinc(II) and nickel(II) tetraazamacrocyclic complexes”. Inorganic Chemistry8 (1989):1476-1480.
  17. Hubin TJ., et al. “Synthesis, structure, and stability in acid of copper(II) and zinc(II) complexes of cross-bridged tetraazamacrocycles”. InorganicaChimica Acta 348(2003):33-40.
  18. Yasmin S., et al. “Three transition-metal complexes with the macrocyclic ligand meso 5,7,7,12,14,14,-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L):[Cu(ClO4)2(L)], [Zn(NO3)2(L)] and [CuCl(L)(H2O)]Cl”. Acta Crystallography C69 (2013):862-867.
  19. Yasmin S., et al. “Synthesis, characterization and antimicrobial studies of zinc(II) complexes with hexamethyl-tetraazacyclotetradecadiene Me6[14]diene (L) and C-chiral isomers of its reduced analogue”. Journal of Inclusion Phenomena and Macrocyclic Chemistry 87 (2017):239-250.
  20. Barua S., et al. “Palladium complexes with hexamethyltetraazacyclotetradecadiene (L) and isomers of its reduced form (‘tet-a’ & ‘tet-b’):synthesis, characterization and antimicrobial studies”.Journal of Inclusion Phenomena and Macrocyclic Chemistry 86 (2016):291-303.
  21. Biswas FB., et al. “An in vitro antibacterial and antifungal effects of cadmium(II) complexes of hexamethyltetraazacyclotetradecadiene ligands”. Asian Pacific Journal Tropical Biomedicine 4 (2014):S618-S623.
  22. Curtis NF and HayRW. “A novel heterocycle synthesis. Formation of 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradeca-4,11-diene dihydroperchlorate by reaction of diaminoethanemonohydroperchlorate with mesityl oxide or acetone”. Chemical Communications (1966): 524-525.
  23. Hay RW, et al. “A Convenient Synthesis of the Tetra-aza-macrocyclic Ligands trans-[14]-Diene, Tet a, and Tet b”. Journal of Chemical Society Perkin Trans1(1975): 591-593.
  24. Roy TG., et al. “Axial ligand substitution in diastereoisomeric trans-[Co(Me8[14]ane)Cl2]+ Complexes and their anti-fungal activities”. Journal of Coordination Chemistry 59(3) (2006): 351-362.
  25. Hassu RL and Burmeister JL. “Solvent control of the bonding mode of co-ordinatedthiocyanate ion in cobalt(III) complexes”. Chemical Communications (1971): 568.
  26. Farago ME and James JM., “Coordination of Thiocyanate and Selenocyanate in Some Diamine Complexes of Nickel(II) and Copper(II)” Inorganic chemistry 4(1965):1706-1711.
  27. Sabatini A and Bertin I “Infrared Spectra between 100 and 2500 Cm.-1 of Some Complex Metal Cyanates, Thiocyanates, and Selenocyanates”.Inorganic chemistry 4(1965):959.
  28. Roy TG., et al. “Synthesis, characterization and antifungal activities of some new copper(II) complexes of octamethyltetraazacyclotetradecadiene”.Metal Based Drugs6 (1999):345-354.
  29. Roy TG. “Synthesis, Characterisation and antimicrobial activities of some copper(II) and nickel(II) complexes of hexamethyltetraaza-cyclotetradecadiene, Me6[14]diene and their substitution products”. The Chittagong University Journal of Science 35(2012): 122-142.
  30. Bembi R., et al. “ 9.Characterization of diastereoisomeric trans-(Co(Me8[14]ane)Cl2]+ complexes”. Inorganic Chemistry 30(1991):1403-1406.
  31. Hay RW., et al. “Characterization of cis-[CoCl2L]+ and two diastereoisomeric trans-[CoCl2L]+ complexes and studies of the aquation kinetics (L=C-meso-5,12-dimethyl-1,4,8,11-tetra-azacyclotetradecane)”.Dalton Transaction (1984):1921-1925.
  32. Roy TG., et al. “trans(5,7, 7, 12, 14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca4,11-diene-қ4 N, N′,N′′,N′′′,N′′′′)bis(nitrite-қN)-cobalt(III) perchlorate hemihydrates”. Acta Crystallography E67(2011): 1576-1577.
  33. Greenwood NN., et al. “Behaviour of tellurium(IV) chloride, bromide, and iodide in organic solvents and the structures of the species present”. Journal of Chemical Society A, (1968): 2209-2212.
  34. Roy TG. “Axial addition in diastereoisomeric [Cu(Me8[14]ane)](ClO4)2] complexes: anti-fungal and antibacterial activities”. Journal of Coordination Chemistry59(2006) 1757-1767.
  35. Roy TG., et al. “Copper(II) and nickel(II) complexes of N, N-bis(2-hydroxyethyl)-octamethyl-1,4,8,11-tetraaza-cyclotetradecan”. European Journal of Inorganic Chemistry (2004):4115-4123.
  36. Roy TG., et al. “Synthesis, electrolytic behaviour and antimicrobial activities of cadmium Complexes of isomers of 3,10-C-meso- 3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane”. Journal of Coordination Chemistry 40 (2007): 1567-1578.
  37. Salehi M and Hasanzadeh M. “Characterization, crystal structures, electrochemical and antibacterial studies of four new binuclear cobalt(III) complexes derived from o-aminobenzyl alcohol”. InorganicaChimicaActa 426(2015): 6-14.
  38. Dharmaraj N., et al. “Ruthenium(II) complexes containing bidentate Schiff bases and their antifungal activity”. Transition Metal Chemistry 26(2001):105-109.


Citation: Tapashi Ghosh Roy., et al. “Tetraazamacrocyclic Ligands and their Zinc(II) Complexes: Synthesis, Characterization and Biological Activities". Acta Scientific Pharmaceutical Sciences 4.8 (2020): 42-54.


Acceptance rate32%
Acceptance to publication20-30 days

Indexed In

News and Events

  • Certification for Review
    Acta Scientific certifies the Editors/reviewers for their review done towards the assigned articles of the respective journals.
  • Submission Timeline for Upcoming Issue
    The last date for submission of articles for regular Issues is May 30, 2024.
  • Publication Certificate
    Authors will be issued a "Publication Certificate" as a mark of appreciation for publishing their work.
  • Best Article of the Issue
    The Editors will elect one Best Article after each issue release. The authors of this article will be provided with a certificate of "Best Article of the Issue"
  • Welcoming Article Submission
    Acta Scientific delightfully welcomes active researchers for submission of articles towards the upcoming issue of respective journals.

Contact US