Fe and Mn complexes based on 2,4,6-tris(2-pyridyl)-triazine: synthesis, structures, magnetic and biological properties

Reaction of the polypyridyl ligand 2,4,6-tris(2-pyridyl)- s -triazine (tpt) with mono- and polynuclear Fe( iii ) or Mn( ii ) precursors, specifically tri- or hexanuclear Fe( iii ) pivalates (piv − ), [Mn 6 O 2 (piv) 10 (Hpiv) 4 ] and Mn( ii ) isobutyrate (ib − ), in various solvents and under various reaction conditions showcase the ligand's surprising coordination characteristics. The reactions result in mononuclear [Fe III (tpt)(tptH)][Fe III Cl 4 ] 4 ·2(thf)·0.23(H 2 O) ( 1 ), [Fe III (piv)(tpt)Cl 2 ] ( 2 ), [Fe II (tpt)Cl 2 ]·2(H 2 O) ( 3a ), dinuclear [Fe III 2 O(tpt) 2 Cl 4 ] ( 3 ), and heptanuclear [Fe III 7 O 4 (piv) 12 (tpt-O)]·A [A = MeCN ( 4a ) or 4(dioxane) ( 4b )] and [Fe III 7 O 4 (piv) 11 (tpt-O)(i-PrO)(i-PrOH)]·0.75(i-PrOH) ( 5 ), as well as the mononuclear compounds [Mn II (tpt)(NO 3 )(H 2 O) 2 ](NO 3 ) ( 6 ) and [Mn II (tpt)(ib)(Cl)(MeOH)]·MeOH ( 7 ). Single-crystal X-ray diffraction analyses identify tpt as a tridentate NNN donor ligand that forms two five-membered metallocycles in 1-3 , 6 and 7 , whereas in 4 and 5 five tpt N atoms form coordinative bonds accompanied by an unusual metal-induced oxidation of one of the carbon atoms of the central triazine core. Magnetic properties of Fe( iii )-tpt ( 2-5 ), Fe( ii )-tpt ( 3a ), and Mn( ii )-tpt ( 7 ) compounds show dominant antiferromagnetic coupling for polynuclear coordination cluster compounds. The Mn( ii )-tpt complexes 6 and 7 exhibit efficient catalytic properties in the production of enzymes by microorganisms, which concerns the synthesis of exocellular proteases in Fusarium gibbosum CNMN FD 12 or Trichoderma koningii Oudemans CNMN FD 15 fungi strains. Thus, compounds 6 and 7 can be used for producing proteolytic enzymes with wide applications including in the food, detergents and pharmaceutical industries. 2,4,6-Tris(2-pyridyl)-triazine induces not only the condensation of heptameric coordination clusters with iron oxo cores but also undergoes triazine oxidation, adding an O donor site.