title: From hydrated Ni3(OH)2(C8H4O4)2(H2O)4 to anhydrous Ni2(OH)2(C8H4O4): impact of structural transformations on magnetic properties.
abstract: Dehydration of the hybrid compound [Ni3(OH)2(tp)2(H2O)4] (1) upon heating led to the sequential removal of coordinated water molecules to give [Ni3(OH)2(tp)2(H2O)2] (2) at T1 = 433 K and thereafter anhydrous [Ni2(OH)2(tp)] (3) at T2 = 483 K. These two successive structural transformations were thoroughly characterized by powder X-ray diffraction assisted by density functional theory calculations. The crystal structures of the two new compounds 2 and 3 were determined. It was shown that at T1 (433 K) the infinite nickel oxide chains built of the repeating structural unit [Ni3(μ3-OH)2](4+) in 1 collapse and lead to infinite porous layers, forming compound 2. The second transformation at T2 (483 K) gave the expected anhydrous compound 3, which is isostructural with Co2(OH)2(tp). These irreversible transitions directly affect the magnetic behavior of each phase. Hence, 1 was found to be antiferromagnetic at TN = 4.11 K, with metamagnetic behavior with a threshold field Hc of ca. 0.6 T. Compound 2 exhibits canted antiferromagnetism below TN = 3.19 K, and 3 is ferromagnetic below TC = 4.5 K.
authors.affiliation: Institut Jean Lamour, UMR 7198 CNRS, Université de Lorraine , BP 70239, rue du Jardin Botanique, 54506 Vandoeuvre lès Nancy, France.
authors.forename: Adel
authors.initials: A
authors.lastname: Mesbah
authors.forename: Pierre
authors.initials: P
authors.lastname: Rabu
authors.forename: Romain
authors.initials: R
authors.lastname: Sibille
authors.forename: Sébastien
authors.initials: S
authors.lastname: Lebègue
authors.forename: Thomas
authors.initials: T
authors.lastname: Mazet
authors.forename: Bernard
authors.initials: B
authors.lastname: Malaman
authors.forename: Michel
authors.initials: M
authors.lastname: François