Selective Recognition of Different Tartratogermanate Anions using 1,10‐phenantroline Complexes of Fe(II), Co(II), Ni(II)

Abstract

This study describes synthesis and structure features of new heterometallic mixed‐ligand cation‐anionic complexes {[Fe(phen)3][Ge2(OH)2(μ‐Tart)2]}2 ⋅ 13H2O(I), [Co(phen)3]2[{Ge2(OH)(H2Tart)(μ‐Tart)2}Cl] ⋅ 11H2O(II), [Ni(phen)3][Ge2(OH)2(μ‐Tart)2] ⋅ 5H2O(III), [Ni(phen)3]2[{Ge2(OH)(H2Tart)(μ‐Tart)2}Cl] ⋅ 11H2O(IV) (Tart ‐ tartaric acid, phen ‐ 1,10‐phenantroline)‐potential drugs, nutritional supplements and growth stimulants. Two forms of tartratogermanate anions are selectively recognized using Fe (II), Co (II), Ni (II) 1,10‐phenantroline cations as receptors. The [Ge2(OH)2(μ‐Tart)2]2− (I, III) contains two Ge atoms bounded by two bridging tartaric acids, the coordination polyhedron of both five‐coordinated Ge atoms is a trigonal bipyramid, while in the [Ge2(OH)(H2Tart)(μ‐Tart)2]3− (II, IV) two Ge atoms have different coordination polyhedrons ‐ trigonal bipyramid and distorted octahedron, formed through the additional terminal tartaric acid. Cations with the common formula [Me(phen)3]2+ (Me=Co, Fe, Ni) form the coordination polyhedron octahedron.

Supramolecular Salts of Germanium (IV) with Tartaric Acid, Zinc and 1,10‐Phenanthroline/2,2‘‐Bipyridine: Synthesis, Structural Features and Selective Recognition

“…The geometry index τ5 is 0.9 for all trigonal bipyramidal structures [25] . The structure of anions in complex compounds 1 and 2 is in good agreement tartratogermanate anions with described earlier [10–15] …”

“…Combination of such structural units promotes better complexation and prevents competitive binding since metals combine with different ligands. Previously authors succeeded to obtain a set of new supramolecular architectures in which d‐metals (Co, Ni, Fe, Cu), that do not only potentiate the activity of Ge, but also, in the form of 1,10‐phenanthroline, 2,2’‐bipyridine complexes, act as receptors for different tartratogermanate anions and selectively recognize them from the reaction media [10–15] . The modification of the substrate specificity continues to be one of the most attractive fields in supramolecular chemistry and is widely applied in sensing, extraction, self‐assembly, and enzymatic catalysis [16–20] .…”

Supramolecular Salts of Fe(II)/Co(II)/Ni(II)/Cu(II)/Zn(II) 1,10‐Phenanthroline Cations and Similar Complex Tartratostannate(IV) Anions: From Structural Features to Antimicrobial Activity and Enzyme Activation

“…The diversity of bioligands, metal ions, ability to combine them in the mixed‐ligand, heterometallic complexes with variable coordination geometry leads to the development of complex compounds with novel modes of biological action [7–11] . From this point of view, list of the complexing agents is constantly enlarged and includes novel ions such as tin(IV) and d‐metals [12–16] . In the framework of the systematic research in the field of biocoordination chemistry of Germanium(IV) and Tin(IV), [17–20] authors have previously described complex isostructural cation‐anionic compounds [M(phen) 3 ] 2 [Sn 2 (μ‐Tart) 2 (H 2 Tart) 2 ], that combine with the widely used antimicrobial agents: 1,10‐phenanthroline (phen), d‐metal (M=Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), tin and polydentate tartaric acid (H 4 Tart).…”

“…[7][8][9][10][11] From this point of view, list of the complexing agents is constantly enlarged and includes novel ions such as tin(IV) and d-metals. [12][13][14][15][16] In the framework of the systematic research in the field of biocoordination chemistry of Germanium(IV) and Tin(IV), [17][18][19][20] authors have previously described complex isostructural cation-anionic compounds [M(phen) 3 ] 2 [Sn 2 (μ-Tart) 2 (H 2 Tart) 2 ], that combine with the widely used antimicrobial agents: 1,10-phenanthroline (phen), d-metal (M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), tin and polydentate tartaric acid (H 4 Tart). These compounds appear to be promising drugs with high biological activity due to the possible synergism of the components and increasing number of inhibition and activation mechanisms.…”

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“…In the framework of this study, compounds that include two diff erent metals with unlike coordination shells and consist of separate cations and anions are considered the most perspective due to the synergism of their components and variability of action mechanisms [12,13]. Previously the authors have developed a novel synthesis strategy that involves a combination of essential Ge(IV) with tartaric acid as an anion and Fe(II)/ Co(II)/ Ni(II)/ Cu(II) with biologically active 1,10-phenanthroline/2,2ʹ-bipyridine as a cation, which form double coordination compounds using electrostatic, π-π stacking in-teractions and hydrogen bonds [14][15][16][17][18]. Germanium is characterized by anticarcinogenic, antimicrobial, and antioxidant activities and plays an important role in oxygen transfer, while dicarbonic dihydroxy tartaric acid (H 4 Tart) is a strong chelating agent, widely used in the food industry and pharmacy [19,20].…”