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Preparation of Crystalline Phases of 3D Coordination Polymers Based on Tetracarbonatodiruthenium Units and Lanthanide(III) Ions – Magnetic Characterization
Author(s) -
DelgadoMartínez Patricia,
GonzálezPrieto Rodrigo,
Herrero Santiago,
JiménezAparicio Reyes,
Perles Josefina,
Priego José L.,
Torres M. Rosario,
Sufrate Berta
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700281
Subject(s) - lanthanide , chemistry , yield (engineering) , crystallography , antiferromagnetism , solvothermal synthesis , ion , single crystal , crystal structure , magnetic susceptibility , crystal engineering , supramolecular chemistry , materials science , organic chemistry , condensed matter physics , physics , metallurgy
Attempts to obtain pure crystalline phases of heteropolynuclear diruthenium–lanthanide complexes were made through four different experimental procedures: a conventional method, solvothermal synthesis, solvothermal synthesis assisted by microwave irradiation and layering synthesis. The complexes [Ln(H 2 O) 4 ][Ru 2 (CO 3 ) 4 (H 2 O)] · x H 2 O [Ln = Gd, x = 2.5 ( 1 ); Ln = Nd, x = 4 ( 2 ); Ln = Eu, x = 2.25 ( 3 ); Ln = Yb, x = 2.5 ( 4 )] were obtained in good yields through the different procedures, but the layering method was the best to yield single crystals of 1 , 3 and 4 . In the solvothermal synthesis of 1 , the minor product K 3 [Gd(H 2 O) 4 ] 2 [Ru 2 (CO 3 ) 4 ] 3 · 3.5H 2 O ( 5 ) was also obtained in a very low yield. The crystal structures of the three‐dimensional compounds 1 and 3 – 5 were determined by single‐crystal X‐ray diffraction, and two different structural types were found for the Gd derivatives. The magnetic properties of 1 , 2 and 4 were fitted with an equation including the sum of the molar susceptibilities of the diruthenium unit and the lanthanide ion. However, the fit of the magnetic properties of 3 requires the consideration of the existence of the splitting of the 7 F ground‐state term by spin–orbit coupling. This study shows that the magnetic behaviours of 1 , 2 and 4 are governed by weak antiferromagnetic interactions between the diruthenium units and the lanthanide ions.