Versatile Reactivity of Mn<sup>II</sup> Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates
Ruslan A. Polunin,
Igor S. Evstifeev,
Olivier Cador,
Stéphane Golhen,
Konstantin S. Gavrilenko,
Anton S. Lytvynenko,
Nikolay N. Efimov,
Vadim V. Minin,
Artem S. Bogomyakov,
Lahcène Ouahab,
Sergey V. Kolotilov,
Mikhail A. Kiskin,
Igor L. Eremenko
Affiliations
Ruslan A. Polunin
L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028 Kiev, Ukraine
Igor S. Evstifeev
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russia
Olivier Cador
University of Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)–UMR 6226, F-35000 Rennes, France
Stéphane Golhen
University of Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)–UMR 6226, F-35000 Rennes, France
Konstantin S. Gavrilenko
Research-And-Education ChemBioCenter, National Taras Shevchenko University of Kyiv, Chervonotkatska str., 61, 03022 Kiev, Ukraine
Anton S. Lytvynenko
L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028 Kiev, Ukraine
Nikolay N. Efimov
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russia
Vadim V. Minin
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russia
Artem S. Bogomyakov
International Tomography Center, Siberia Branch of Russian Academy of Science, Institutskaya str. 3a, 630090 Novosibirsk, Russia
Lahcène Ouahab
University of Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)–UMR 6226, F-35000 Rennes, France
Sergey V. Kolotilov
L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028 Kiev, Ukraine
Mikhail A. Kiskin
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russia
Igor L. Eremenko
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russia
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).
