title: Heterometallic Coordination Polymers Assembled from Trigonal Trinuclear Fe2Ni-Pivalate Blocks and Polypyridine Spacers: Topological Diversity, Sorption, and Catalytic Properties.
abstract: Linkage of the trigonal complex [Fe2NiO(Piv)6] (where Piv(-) = pivalate) by a series of polypyridine ligands, namely, tris(4-pyridyl)triazine (L(2)), 2,6-bis(3-pyridyl)-4-(4-pyridyl)pyridine (L(3)), N-(bis-2,2-(4-pyridyloxymethyl)-3-(4-pyridyloxy)propyl))pyridone-4 (L(4)), and 4-(N,N-diethylamino)phenyl-bis-2,6-(4-pyridyl)pyridine (L(5)) resulted in the formation of novel coordination polymers [Fe2NiO(Piv)6(L(2))]n (2), [Fe2NiO(Piv)6(L(3))]n (3), [Fe2NiO(Piv)6(L(4))]n·nHPiv (4), and [{Fe2NiO(Piv)6}4{L(5)}6]n·3nDEF (5, where DEF is N,N-diethylformamide), which were crystallographically characterized. The topological analysis of 3, 4, and 5 disclosed the 3,3,4,4-connected 2D (3, 4) or 3,4,4-connected 1D (5) underlying networks which, upon further simplification, gave rise to the uninodal 3-connected nets with the respective fes (3, 4) or SP 1-periodic net (4,4)(0,2) (5) topologies, driven by the cluster [Fe2Ni(μ3-O)(μ-Piv)6] nodes and the polypyridine μ3-L(3,4) or μ2-L(5) blocks. The obtained topologies were compared with those identified in other closely related derivatives [Fe2NiO(Piv)6(L(1))]n (1) and {Fe2NiO(Piv)6}8{L(6)}12 (6), where L(1) and L(6) are tris(4-pyridyl)pyridine and 4-(N,N-dimethylamino)phenyl-bis-2,6-(4-pyridyl)pyridine, respectively. It was shown that a key structure-driven role in defining the dimensionality and topology of the resulting coordination network is played by the type of polypyridine spacer. Compounds 2 and 3 possess a porous structure, as confirmed by the N2 and H2 sorption data at 78 K. Methanol and ethanol sorption by 2 was also studied indicating that the pores filled by these substrates did not induce any structural rearrangement of this sorbent. Additionally, porous coordination polymer 2 was also applied as a heterogeneous catalyst for the condensation of salicylaldehyde or 9-anthracenecarbaldehyde with malononitrile. The best activity of 2 was observed in the case of salicylaldehyde substrate, resulting in up to 88% conversion into 2-imino-2H-chromen-3-carbonitrile.
authors.affiliation: †L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev 03028, Ukraine.
authors.forename: Svetlana A
authors.initials: SA
authors.lastname: Sotnik
authors.affiliation: †L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev 03028, Ukraine.
authors.forename: Ruslan A
authors.initials: RA
authors.lastname: Polunin
authors.affiliation: ‡N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 GSP-1 Moscow, Russian Federation.
authors.forename: Mikhail A
authors.initials: MA
authors.lastname: Kiskin
authors.affiliation: §Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Kirillov
authors.affiliation: †L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev 03028, Ukraine.|∥Research-And-Education ChemBioCenter, National Taras Shevchenko University of Kyiv, Chervonotkackaya str., 61, Kiev 03022, Ukraine.
authors.forename: Victoria N
authors.initials: VN
authors.lastname: Dorofeeva
authors.affiliation: ∥Research-And-Education ChemBioCenter, National Taras Shevchenko University of Kyiv, Chervonotkackaya str., 61, Kiev 03022, Ukraine.|⊥Enamine Ltd., A. Matrosova str. 23, Kiev 01103, Ukraine.
authors.forename: Konstantin S
authors.initials: KS
authors.lastname: Gavrilenko
authors.affiliation: ‡N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 GSP-1 Moscow, Russian Federation.
authors.forename: Igor L
authors.initials: IL
authors.lastname: Eremenko
authors.affiliation: ‡N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 GSP-1 Moscow, Russian Federation.
authors.forename: Vladimir M
authors.initials: VM
authors.lastname: Novotortsev
authors.affiliation: †L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev 03028, Ukraine.
authors.forename: Sergey V
authors.initials: SV
authors.lastname: Kolotilov