Design and synthesis of copper(II) malonates with N,N’-containing linkers

Zorina-Tikhonova, E.N.; Chistyakov, A.S.; Novikova, V.A.; Knyazev, D.A.; Gogoleva, N.V.; Blinou, D.O.; Efimov, N.N.; Dorovatovskii, P.; Kiskin, M.A.; Eremenko, I.L.; Vologzhanina, A.V.

Авторы: Zorina-Tikhonova Ekaterina N., Chistyakov Aleksandr S., Novikova Veronika A., Knyazev Daniil A., Gogoleva Natalia V., Blinou Daniil O., Efimov N.N., Dorovatovskii Pavel, Kiskin Mikhail A., Eremenko Igor L., Vologzhanina Anna V.
Журнал: CrystEngComm
Том: 2025
Год издания: 2023
Издательство: Royal Society of Chemistry
Местоположение издательства: United Kingdom
DOI: 10.1039/d3ce00081h
Аннотация: Knowledge-based approach to the design of coordination polymers with a given architecture in general requires knowledge of regularities between the local coordination of metal atoms (or polynuclear metal-containing units), coordination modes of all ligands in a complex, and the entire framework topology. The effect of the local coordination on the dimensionality and topology of the underlying nets was demonstrated on the example of 4,4′-bipyridine (bipy), 1,2-bis(4-pyridyl)ethylene (bpe) and 1,2-bis(4-pyridyl)ethane (bpa) containing copper(II) malonates. The most abundant networks were evaluated for these compounds and compared with those for previously analyzed and synthesized zinc(II)-containing analogs. Eight novel complexes, namely [Cu(bpe)(mal)]·2CH3CN, [Cu4(bipy)4(Me2mal)4(H2O)5]·3H2O, [Cu(bpe)(HMe2mal)2]·H2O, [Cu(bpe)(Me2mal)]·H2O, [Cu4(bpe)3(Et2mal)4]·5H2O, [Cu4(bpa)3(Et2mal)4]·5.5H2O, [Cu(bpe)(Amal)]·0.25H2O, and [Cu(bpa)(Amal)]·0.25H2O (H2mal = malonic acid, H2Me2mal = dimethylmalonic acid, H2Et2mal = diethylmalonic acid, H2Amal = allylmalonic acid), were synthesized and characterized. Four of them realized the square lattice topology (sql) of their underlying nets, which is highly abundant for copper(II) malonates with N,N′-containing linkers but rarely occurs in similar complexes based on other transition metals. The UV-sensitivity of the bpe-containing complexes as well as of the previously reported complex [Cu4(bpe)3(mal)4]·6H2O was studied; and [Cu4(bpe)3(mal)4]·6H2O was found to undergo a single-crystal-to-single-crystal photoinitiated [2 + 2] cycloaddition reaction to [Cu4(bpe)(tpcb)(mal)4]·6H2O (tpcb = rctt-1,2,3,4-tetrakis(pyridin-4-yl)cyclobutane). The dc-magnetic measurements of the complexes [Cu(bpe)(Me2mal)]·H2O, [Cu(bpe)(Amal)]·0.25H2O and [Cu(bpa)(Amal)]·0.25H2O indicated the presence of very weak antiferromagnetic intermolecular interactions. Using EPR spectroscopy, it was shown that the distortion of the polyhedron of the copper(II) atom corresponded to a change in the anisotropy of the g-tensor.
Добавил в систему: Вологжанина Анна Владимировна

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Design and synthesis of copper(II) malonates with N,N’-containing linkersстатья

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