Solvent effect in the chemical design of coordination polymers of various topologies with Co2+ and Ni2+ ions and 2-furoate anions†
*a
Irina A.
Lutsenko,
a
Konstantin A.
Babeshkin,
a
Andrey V.
Sokolov,
b
Eugeny V.
Alexandrov,
b
Nikolay N.
Efimov,
a
Maxim A.
Shmelev,
a
Andrey V.
Khoroshilov,
a
Igor L.
Eremenko
a
and
Mikhail A.
Kiskin
a
Abstract
Four new frameworks were obtained by slow diffusion of a ligand solution – 1,2-bis(4-pyridyl)ethylene (dpe) into solutions of NiII and CoII furoates. It is shown that, depending on the combination of solvents used, it is possible to purposefully set the topology of the coordination polymers as a simple chain in [Co(fur)2(dpe)(CH3OH)2]n (1), 2D 4-c sql in [Co(fur)2(dpe)2]n (2)/[Ni(fur)2(dpe)2]n (3) and 3D 3-cetb in [Ni(fur)2(dpe)1.5(H2O)]n·3H2O (4) (fur− is the anion of 2-furoic acid). The simple chains extend in two different directions. The sql nets show inclined polycatenation. Compound 4 exhibits the first example of such a high degree of interpenetration as 7, which is more than three times higher than the known record for nets. All the compounds were characterized by single crystal X-ray analysis. The metal atoms in the structural fragments have a CN = 6 and are in an octahedral environment with a different ratio of N and O – ({CoO4N2} (1), {MO2N4} for M = Co (2) and Ni (3), {NiO3N3} (4)). The coordination network of 4 has accessible channels with an estimated pore volume of 4650 Å3 per unit cell (29.4%). Thermal behavior of 1, 3 and 4 was studied by simultaneous thermal analysis (STA). The obtained χT(T) dependences were approximated using the PHI software. It was shown that interweaving results in the shortening of the metal–metal magnetic interactions.
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