期刊
INORGANIC CHEMISTRY
卷 51, 期 20, 页码 11126-11132出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic3016673
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资金
- Spanish Ministerio de Ciencia e Innovacion (MICINN) (presently Ministerio de Economia y Competitividad)
- FEDER funds [CTQ2010-18414, CSD2007-00010, MAT2011-27233-C02-02]
- Generalitat Valenciana [PROMETEO/2012/049, ACOMP2012/233]
Here we describe the synthesis, structure, and magnetic properties of two related coordination polymers made up of self-assembling Fe(II) ions, pyrazine (pz), and the tetrathiocyanopalladate anion. Compound {Fe(MeOH)(2)[Pd(SCN)(4)])center dot pz (1a) is a two-dimensional coordination polymer where the Fe(II) ions are equatorially coordinated by the nitrogen atoms of four [Pd(SCN)(4)](2-) anions, each of which connects four Fe(II) ions, forming corrugated layers {Fe[Pd(SCN)(4)]}. The coordination sphere of Fe(II) is completed by the oxygen atoms of two CH3OH molecules. The layers stack one on top of each other in such a way that the included pz molecule establishes strong hydrogen bonds with the coordinated methanol molecules of adjacent layers. Compound {Fe(pz)[Pd(SCN)(4)]} (2) is a three-dimensional porous coordination polymer formed by flat {Fe[Pd(SCN)(4)]}(infinity) layers pillared by the pz ligand. Thermal analysis of la shows a clear desorption of the two coordinated CH3OH molecules giving a rather stable phase (1b), which presumably is a polymorphic form of 2. The magnetic properties of the three derivatives are typical of the high-spin Fe(II) compounds. However, compounds 1b and 2, with coordination sphere [FeN6], show thermal spin crossover behavior at pressures higher than ambient pressure (10(5) MPa).
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