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. 2021 Feb 15;26(4):1021.
doi: 10.3390/molecules26041021.

Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates

Ruslan A Polunin  1 , Igor S Evstifeev  2 , Olivier Cador  3 , Stéphane Golhen  3 , Konstantin S Gavrilenko  4   5 , Anton S Lytvynenko  1 , Nikolay N Efimov  2 , Vadim V Minin  2 , Artem S Bogomyakov  6 , Lahcène Ouahab  3 , Sergey V Kolotilov  1 , Mikhail A Kiskin  2 , Igor L Eremenko  2
Affiliations

Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates

Ruslan A Polunin et al. Molecules. .

Abstract

Reaction of 2,2'-bipyridine (2,2'-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)2(EtOH)]n led to the formation of binuclear complexes [Mn2(Piv)4L2] (L = 2,2'-bipy (1), phen (2); Piv- is the anion of pivalic acid). Oxidation of 1 or 2 by air oxygen resulted in the formation of tetranuclear MnII/III complexes [Mn4O2(Piv)6L2] (L = 2,2'-bipy (3), phen (4)). The hexanuclear complex [Mn6(OH)2(Piv)10(pym)4] (5) was formed in the reaction of [Mn(Piv)2(EtOH)]n with pyrimidine (pym), while oxidation of 5 produced the coordination polymer [Mn6O2(Piv)10(pym)2]n (6). Use of pyrazine (pz) instead of pyrimidine led to the 2D-coordination polymer [Mn4(OH)(Piv)7(µ2-pz)2]n (7). Interaction of [Mn(Piv)2(EtOH)]n with FeCl3 resulted in the formation of the hexanuclear complex [MnII4FeIII2O2(Piv)10(MeCN)2(HPiv)2] (8). The reactions of [MnFe2O(OAc)6(H2O)3] with 4,4'-bipyridine (4,4'-bipy) or trans-1,2-(4-pyridyl)ethylene (bpe) led to the formation of 1D-polymers [MnFe2O(OAc)6L2]n·2nDMF, where L = 4,4'-bipy (9·2DMF), bpe (10·2DMF) and [MnFe2O(OAc)6(bpe)(DMF)]n·3.5nDMF (11·3.5DMF). All complexes were characterized by single-crystal X-ray diffraction. Desolvation of 11·3.5DMF led to a collapse of the porous crystal lattice that was confirmed by PXRD and N2 sorption measurements, while alcohol adsorption led to porous structure restoration. Weak antiferromagnetic exchange was found in the case of binuclear MnII complexes (JMn-Mn = -1.03 cm-1 for 1 and 2). According to magnetic data analysis (JMn-Mn = -(2.69 ÷ 0.42) cm-1) and DFT calculations (JMn-Mn = -(6.9 ÷ 0.9) cm-1) weak antiferromagnetic coupling between MnII ions also occurred in the tetranuclear {Mn4(OH)(Piv)7} unit of the 2D polymer 7. In contrast, strong antiferromagnetic coupling was found in oxo-bridged trinuclear fragment {MnFe2O(OAc)6} in 11·3.5DMF (JFe-Fe = -57.8 cm-1, JFe-Mn = -20.12 cm-1).

Keywords: coordination polymers; magnetic properties; manganese; polynuclear complexes; porous materials; pyridines.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Formulae of pivatale (Piv−) and N-donor ligands used in the study.
Figure 1
Figure 1
Scheme illustrating the formation of complexes 1–11. 2,2′-bipy is 2,2′-bipyridine, 4,4′-bipy is 4,4′-bipyridine, bpe is 1,2-bis-trans-(4-pyridyl)ethylene, pym = pyrimidine, pz = pyrazine. M(Piv)2 in the center of the scheme means [Mn(Piv)2(EtOH)]n or Ni(Piv)2(H2O)2 or [Co(Piv)2]n.
Figure 2
Figure 2
The molecular structures of 1 ((a), atoms with an additional character in the atom labels are at (1 − x, 1 − y, 2 − z)) and 2 ((b), atoms with an additional character in the atom labels are at (1 − x, y, 1/2 − z))H atoms at carbon atoms are omitted for clarity, the displacement ellipsoids are drawn at the 30% probability level.
Figure 3
Figure 3
, The molecular structure of 3 ((a), atoms with an additional character in the atom labels are at (−x, 1 − y, 1 − z)), intra- (only for 2) and intermolecular (for 1 and 2) π-stacking interaction and formation of supramolecular chain structure in crystal lattices of 1 (a) and 2 (b) (H atoms at carbon atoms and methyl groups of pivalate ions are omitted for clarity, (c) the displacement ellipsoids are drawn at the 30% probability level).
Figure 4
Figure 4
Structures of polynuclear units in 5 (a) and 6 (b) respectively. H atoms at carbon atoms, and methyl (in 5) and tert-butyl (in 6) groups of pivalate ions are omitted for clarity, the displacement ellipsoids are drawn at the 30% probability level).
Figure 5
Figure 5
Fragment of crystal lattice (a) and 2D-grid (b,c) of 7. H atoms at carbon atoms and methyl groups of pivalate ions (in a) are omitted for clarity, the displacement ellipsoids are drawn at the 30% probability level (in a).
Figure 6
Figure 6
The structure of [Mn4Fe2O2(Piv)10(MeCN)2(HPiv)2] in 8 (atoms with an additional character in the atom labels are at (1 − x, y, 1/2 − z)). H atoms at carbon atoms and methyl groups of pivalate ions are omitted for clarity, the displacement ellipsoids are drawn at the 30% probability level.
Figure 7
Figure 7
The structure of {MnFe2O(OAc)6(C5H4N)3} fragment in 10. All hydrogen atoms are omitted for clarity. Only one pyridine ring from each 4,4′-bipy ligand is shown.
Figure 8
Figure 8
A fragment of 1D chain of 9. Hydrogen atoms and solvent are omitted for clarity. Note that one bipy molecule in Fragment A is non-bridging; no coordinated metal ions was deleted for fragment A on the figure.
Figure 9
Figure 9
Fragment of crystal structure of 9. View along crystallographic axes a (a) and b (b). All non-bridging bipy molecules, terminal Fe2MnO(OAc)6(4,4′-bipy)3 blocks, hydrogen atoms and non-coordinated DMF molecules are omitted for clarity.
Figure 10
Figure 10
Fragments of 1D chains of 10 (a) and 11 (b). Hydrogen atoms and non-coordinated solvent molecules are omitted for clarity.
Figure 11
Figure 11
π-stacking interactions between the neighboring chains of 10 (a) and 1D-channels in crystal lattice of 11(-DMF) (b). Hydrogen atoms and solvent molecules are omitted for clarity.
Figure 12
Figure 12
Channels in crystal lattice of 11·3DMF (projection along a axis). Solvent molecules (including coordinated DMF) and hydrogen atoms are omitted for clarity.
Figure 13
Figure 13
TG curve for compound 11·3.5DMF (a) and powder XRD patterns for vacuum-dried at 145 °C sample of 11·3.5DMF and calculated from single-crystal X-ray data for 11 (b).
Figure 14
Figure 14
Sorption isotherms of methanol (a) and ethanol (b) by 11′ at 293 K. Arrows on Figure (a) indicate directions of absorption and desorption.
Figure 15
Figure 15
EPR spectra of polycrystalline samples of 1 (a) and 2 (b) at 293 K (1—experimental, 2—calculated).
Figure 16
Figure 16
χMT vs. T dependencies and the calculated curves (─) for 1 (Υ), 2 (⊄).
Figure 17
Figure 17
χMT vs. T dependence, the calculated curve (─) and coupling scheme within a tetranuclear unit Mn4 for compound 7 2MeCN.
Figure 18
Figure 18
χMT vs. T dependence, the calculated curve (─) and coupling scheme within a trinuclear unit Fe2Mn for compounds 11·3.5DMF.
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