Repozytorium

Structure and magnetic behavior of CuII MOFs supported by 1,2,4-triazolyl-bifunctionalized adamantane scaffold.

Autorzy

Ganna A. Senchyk

Andrey B. Lysenko

Eduard B. Rusanov

Alexander N. Chernega

Julia Jezierska

Konstantin V. Domasevitch

Andrew Ozarowski

Rok wydania

2012

Czasopismo

European Journal of Inorganic Chemistry

Strony

5802-5813

DOI

10.1002/ejic.201200873

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

New triazole‐based CuII metal–organic frameworks, [Cu(tr2ad)(SO4)]·3H2O (1), [Cu3(tr2ad)4(H2O)2(SO4)2]SO4·28H2O (2), [Cu3(tr2ad)4(H2O)4](SiF6)3·16H2O (3), constructed utilizing a rigid adamantane scaffold, tr2ad = 1,3‐bis(1,2,4‐triazol‐4‐yl)adamantane, were prepared hydrothermally, and their crystal structures were determined. The structure of 1 is built up from straight chains of corner‐sharing CuN4O2 octahedra supported by short μ2‐tr (tr = 1,2,4‐triazole) and μ2‐SO42– bridges. The tetradentate character of tr2ad results in the formation of layers. The 2D structures of 2 and 3 consist of discrete secondary building blocks [Cu32N1,N2‐tr)6] with triple [–N–N–] triazole links between the adjacent Cu centers [the Cu‐(tr)‐Cu separations are 3.806 and 3.756 Å for 2 and 3, respectively]. The distorted octahedral N4O2 environment of the peripheral Cu atoms is completed by water molecules and/or terminal sulfate anions. The linear magnetic clusters, which act as nodes, are joined together at average distances of 11.2 and 15.0–15.6 Å into square‐grid‐like networks that exploit the double‐bridging μ3‐ and μ4‐bis(triazole) modules. Uncoordinated counteranions and crystal water molecules fill the interlayer space and channels in the complexes and form extensive H‐bonding patterns. The exchange integrals J1 = 9.8 and J2 ≈ 0 cm–1 for the interaction J1(Ŝ1Ŝ2 + Ŝ2Ŝ3) + J2Ŝ1Ŝ3 were determined for 3 from magnetic susceptibility data and reproduced by a broken‐symmetry DFT calculation. The spin Hamiltonian parameters of 3 were found from high‐field electron paramagnetic resonance (EPR) spectra.

Adres publiczny

https://doi.org/10.1002/ejic.201200873

Strona internetowa wydawcy

onlinelibrary.wiley.com

Podobne publikacje
2006

Coordination diversity of N-phosphoryl-N-phenylthiourea (LH) towards CoII, NiII and PdII cations: crystal structure of ML2-N,S and ML2-O,S chelates.

Sokolov F. D., Zabirov N. G., Yamalieva L. N., Shtyrlin V. G., Garipov R. R., Brusko V. V., Verat A. Y., Baranov S. V., Młynarz Piotr, Głowiak Tadeusz, Kozłowski Henryk

2007

Magnetic interactions in CuII–LnIII cyclic tetranuclear complexes: is it possible to explain the occurrence of SMM behavior in CuII–TbIII and CuII-DyIIII complexes?.

Hamamatsu T., Yabe K., Towatari Masaaki, Osa S., Matsumoto Naohide, Re Nazzareno, Pochaba Andrzej, Mroziński Jerzy, Gallani J.-L., Barla A., Imperia P., Paulsen C., Kappler J.-P.