Repozytorium

New tetracopper(II) cubane cores driven by a diamino alcohol: self-assembly synthesis, structural and topological features, and magnetic and catalytic oxidation properties.

Autorzy

Sara S. P. Dias

Marina V. Kirillova

Vânia André

Julia Kłak

Alexander M. Kirillov

Rok wydania

2015

Czasopismo

Inorganic Chemistry

Numer woluminu

54

Strony

5204-5212

DOI

10.1021/acs.inorgchem.5b00048

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Two new coordination compounds with tetracopper(II) cores, namely, a 1D coordination polymer, [Cu4(μ4-H2edte)(μ5-H2edte)(sal)2]n·10nH2O (1), and a discrete 0D tetramer, [Cu4(μ4-Hedte)2(Hpmal)2(H2O)]·7.5H2O (2), were easily self-assembled from aqueous solutions of copper(II) nitrate, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (H4edte), salicylic acid (H2sal), or phenylmalonic acid (H2pma). The obtained compounds were characterized by IR and electron paramagnetic resonance spectroscopy, thermogravimetric and elemental analysis, and single-crystal X-ray diffraction. In addition to different dimensionalities, their structures reveal distinct single-open [Cu4(μ2-O)(μ3-O)3] (in 1) or double-open [Cu4(μ2-O)2(μ3-O)2] (in 2) cubane cores with 3M4-1 topology. In crystal structures, numerous crystallization water molecules are arranged into the intricate infinite 1D {(H2O)18}n water tapes (in 1) or discrete (H2O)9 clusters (in 2) that participate in multiple hydrogen-bonding interactions with the metal-organic hosts, thus extending the overall structures into very complex 3D supramolecular networks. After simplification, their topological analysis revealed the binodal 6,10- or 6,8-connected underlying 3D nets with unique or rare 6,8T2 topology in 1 and 2, respectively. The magnetic properties of 1 and 2 were investigated in the 1.8-300 K temperature range, indicating overall antiferromagnetic interactions between the adjacent Cu(II) ions within the [Cu4O4] cores. The obtained compounds also act as bioinspired precatalysts for mild homogeneous oxidation, by aqueous hydrogen peroxide at 50 °C in an acidic MeCN/H2O medium, of various cyclic and linear C5-C8 alkanes to the corresponding alcohols and ketones. Overall product yields of up to 21% (based on alkane) were achieved, and the effects of various reaction parameters were studied.

Adres publiczny

http://dx.doi.org/10.1021/acs.inorgchem.5b00048

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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