Abstract In the present study authors establish the influence of complex cation on the structure formation, crystal packing, antimicrobial activity and enzyme activation of the previously described isostructural [M(phen) 3 ] 2 [Sn 2 (μ‐Tart) 2 (H 2 Tart) 2 ] complexes (M(II)=Fe( 1 ), Co( 2 ), Ni( 3 ), Cu( 4 ), Zn( 5 )). Despite the similarity of composition and structure, compounds 1–5 showed different level of antimicrobial activity. A certain pattern in their effectiveness – decreasing of minimal concentrations, resembles the Irving‐Williams series (Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II)) and, according to the crystal field theory, correlates with the thermodynamic stability of octahedral cations [M(phen) 3 ] 2+ . Quantum chemical calculations of cations revealed the insights of the “cations‐cell membranes” interactions and allowed authors to conclude that the cations in compounds 4 and 5 are the most lipophilic, have the highest affinity to the lipophilic cell membrane and, as a result, are more bioactive. It was established that compounds 1 – 5 had a different influence on the activity of studied α‐L‐rhamnosidases Penicillium tardum ІMB F‐100074 and Penicillium restrictum ІMB F‐100139. Correlation of these results with the crystal voids calculations and Hirshfeld surface analysis allow authors to suggest that presence of the bigger number of water molecules, generation of the branched network of hydrogen bonds and formation of active intermediate complex “enzyme – effector – substrate”, leads to the biggest intensification of activation properties for the compounds 2 and 5 .
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