Stabilization of Ni2+ dimers in hexacyano Mo6 cluster-based Prussian blue derivatives: experimental and theoretical investigations of magnetic properties

Stabilization of Ni2+ dimers in hexacyano Mo6 cluster-based Prussian blue derivatives: experimental and theoretical investigations of magnetic properties Full article

Journal

Dalton Transactions
ISSN: 1477-9234 , E-ISSN: 1477-9226

Output data

Year: 2018, Volume: 47, Number: 4, Pages: 1122-1130 Pages count : 9 DOI: 10.1039/c7dt02748f

Authors

Daigre Gilles ¹ , Costuas Karine ¹ , Tarasenko Maria S. ² , Ledneva Alexandra Yu. ² , Naumov Nikolay G. ^2,3 , Lemoine Pierric ¹ , Guizouarn Thierry ¹ , Molard Yann ¹ , Amela-Cortes Maria ¹ , Audebrand Nathalie ¹ , Cordier Stéphane ¹

Affiliations

1	Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, France
2	Nikolaev Institute of Inorganic Chemistry, 3 Acad. Lavrentiev pr., 630090 Novosibirsk, Russia
3	Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia

Herein, two new octahedral molybdenum cyanide cluster compounds, namely [{Ni(NH3)6}4{Ni2(NH3)8}1][Mo6Br6Q2(CN)6]3·12H2O, Q = S (1) and Se (2), have been synthesized as single crystals by slow diffusion of a solution of nickel chloride into aqueous ammonia solutions of a K2Cs2[Mo6Br6Q2(CN)6] molybdenum cyanide cluster-based compound. Both 1 and 2 were structurally characterized by single-crystal X-ray diffraction. They are isostructural and crystallize in the cubic system (Im[3 with combining macron]m (no. 229); Z = 2, a = 18.147(1) Å, and V = 5976(1) Å3 and a = 18.188(2) Å and V = 6016(2) Å3 for 1 and 2, respectively). 1 and 2 are based on the association of [Mo6Bri6Qi2(CN)a6]4− (Q = S, Se) cluster anions with Ni2+ dimer-based cubic [Ni2(NH3)8]4+ and octahedral [Ni(NH3)6]2+ cations. The structure is based on 2-fold interpenetrated [{Ni(NH3)6}4{Ni2(NH3)8}1][Mo6Br6Q2(CN)6]3 frameworks related to each other by [½, ½, ½] translation. The unit cell is based on a body-centered cubic framework of cubic [Ni2(NH3)8]4+. The [Mo6Bri6Qi2(CN)a6]4− (Q = S, Se) cluster units are located in the middle of the edges and at the center of the faces of the cell. The [{Ni(NH3)6}]2+ cations are located at the center of the cubes of the a/2 edge. The dimers [Ni2(NH3)8]4+ are stabilized by hydrogen bonds between the cyanide ligands of the cluster unit and the hydrogen atoms of the ammonia molecules. Both compounds exhibit a weak antiferromagnetic coupling within the [Ni2(NH3)8]4+ dimer entities at low temperatures together with a paramagnetic behavior originating from the cations of the octahedral [{Ni(NH3)6}]2+ complexes.

Daigre G. , Costuas K. , Tarasenko M.S. , Ledneva A.Y. , Naumov N.G. , Lemoine P. , Guizouarn T. , Molard Y. , Amela-Cortes M. , Audebrand N. , Cordier S.
Stabilization of Ni2+ dimers in hexacyano Mo6 cluster-based Prussian blue derivatives: experimental and theoretical investigations of magnetic properties
Dalton Transactions. 2018. V.47. N4. P.1122-1130. DOI: 10.1039/c7dt02748f WOS Scopus OpenAlex

Submitted:	Jul 27, 2017
Accepted:	Dec 5, 2017
Published online:	Dec 6, 2017
Published print:	Jan 28, 2018

Web of science:	WOS:000423465200017
Scopus:	2-s2.0-85041116668
OpenAlex:	W2773342654

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OpenAlex	5
Scopus	5
Web of science	5