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Layered Transition Metal Nitroprussides – Their Preparation, Crystal Structure, and Magnetic Properties
Author(s) -
Gil Diego Mauricio,
Osiry Hernandez,
Rodriguez Alejandro,
LemusSantana Ana Adela,
Carbonio Raúl Ernesto,
Reguera Edilso
Publication year - 2016
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.201501401
Subject(s) - chemistry , crystallography , imidazole , molecule , transition metal , steric effects , stacking , metal , crystal structure , stereochemistry , organic chemistry , catalysis
Divalent transition metal (T) nitroprussides form a series of insoluble coordination compounds, which generally crystallize in 3D frameworks, except for a layered (2D) phase of copper. In this contribution, the preparation of layered phases for T = Mn, Fe, Co, Ni, Zn, and Cd is reported. The incorporation of imidazole (Im) during their preparation by the precipitation method inhibits the coordination of the axial CN groups to the metal T, and layered (2D) structures of formula unit T(Im) 2 [Fe(CN) 5 NO] result. The metal T is found coordinated to the N end of the equatorial CN groups. Imidazole molecules occupy its axial coordination sites. In the interlayer region, imidazole molecules from neighboring layers interact through their dipole and quadrupole moments. The stacking of the aromatic rings from neighboring molecules deviates from the sandwich‐type configuration, which in turn weakens the magnetic interactions between T 2+ cations located in neighboring layers. Axial unbridged CN and NO groups play a steric hindrance role, thus causing a deviation from the sandwich configuration for the aromatic rings. This series of 2D transition metal nitroprussides can be exfoliated by using appropriate solvents, for example, 1‐methyl‐2‐pyrrolidone.