title: Hybrid materials containing organometallic cations and 3-D anionic metal dicyanamide networks of type [Cp*2M][M'(dca)3].
abstract: A new series of hybrid materials of type [Cp*2M][M'(dca)3] has been prepared by cation templation and structurally characterised (M = Fe(III), Co(III); M'= Mn(II), Fe(II), Co(II), Ni(II), Cd(II); dca-= N(CN)2-). The crystallographic analysis of [Cp*2Fe][Cd(dca)(3)] showed that the [Cd(dca)3]- anionic framework is of a symmetrical 3-D alpha-polonium type, containing octahedral Cd nodes and micro (1,5)-dca bridging ligands. The [Cp*2Fe]+ cations occupy the cube-like cavities within the framework. The cationic and anionic-framework sublattices remain magnetically independent and display susceptibilities, over the range 300 to 2 K, of a Curie-Weiss nature obtained by adding a S= 1/2 (Cp*2Fe+) or a S= 0 (Cp*2Co+) contribution to those of the weakly antiferromagnetically coupled frameworks of M'. These hybrid species do not show any intrinsic long-range magnetic order. The present [Cp*2Fe]M'(dca)3] series display the characteristic, unusually shaped [Cp*2Fe]+ Mossbauer line, in the range 295-5 K, assigned (below 101 K) as the sum of a narrow and a broad line. Relaxation effects were evident. The [Fe(dca)3]- compound showed superimposed low-spin Fe(III) and high-spin Fe(II) lines, the latter giving relaxation broadening effects.
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, Dr. Moliner, 50, 46100, Burjassot, Spain.
authors.forename: Patricia M
authors.initials: PM
authors.lastname: Van der Werff
authors.forename: Eugenia
authors.initials: E
authors.lastname: Martínez-Ferrero
authors.forename: Stuart R
authors.initials: SR
authors.lastname: Batten
authors.forename: Paul
authors.initials: P
authors.lastname: Jensen
authors.forename: Catalina
authors.initials: C
authors.lastname: Ruiz-Pérez
authors.forename: Manuel
authors.initials: M
authors.lastname: Almeida
authors.forename: Joao C
authors.initials: JC
authors.lastname: Waerenborgh
authors.forename: John D
authors.initials: JD
authors.lastname: Cashion
authors.forename: Boujemaa
authors.initials: B
authors.lastname: Moubaraki
authors.forename: José Ramón
authors.initials: JR
authors.lastname: Galán-Mascarós
authors.forename: José María
authors.initials: JM
authors.lastname: Martínez-Agudo
authors.forename: Eugenio
authors.initials: E
authors.lastname: Coronado
authors.forename: Keith S
authors.initials: KS
authors.lastname: Murray