0000000000406683
AUTHOR
Michael Menzel
Molecular switching complexes with iron and tin as central atom
Abstract The precursor [Fe III (L)Cl] (LH 2 = N , N ′-bis(2′-hydroxy-benzyliden)-1,6-diamino-3-N-hexane is a high-spin ( S = 5/2) complex. This precursor is combined with the bridging units [Sn IV (X) 4 ] (X = CN − , NCS − ) to yield star-shaped pentanuclear clusters, [(LFe III –X) 4 Sn]Cl 4 . For X = CN − the 57 Fe-Mossbauer data show a multiple spin transition between iron(III) in the high-spin and low-spin state, while the 119m Sn-Mossbauer data indicate a valence tautomerism between Sn(IV) and Sn(II). Changing the bridging unit from X = CN − to X = NCS − turns the switchability off.
Spin transition in heptanuclear star-shaped iron(III)–antimony(V) NCS- and CN-bridged compounds
Abstract The precursor [FeIII(L)Cl] (LH2 = N,N′-bis(2′-hydroxy-benzyliden)-1,6-diamino-3-azahexane) has been prepared and Mossbauer spectroscopy assigned a high-spin (S = 5/2) state at room temperature. The precursor is combined with the bridging units [SbV(X)6]− (X = CN−, NCS−) to yield star-shaped heptanuclear clusters [(LFeIII–X)6SbV]Cl5. The star-shaped compounds are in general high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers switch to the low-spin state as indicated by Mossbauer spectroscopy, i.e. multiple electronic transitions. While the cyano-bridged complex performs a multiple spin transition the thiocyanate-compound shows no significant popul…
The solid-state architecture of a metallosupramolecular polyelectrolyte
Self-assembly of Fe(II) and the ditopic ligand 1,4-bis(2,2′:6′,2″-terpyridine-4′-yl)benzene results in equilibrium structures in solutions, so-called metallosupramolecular coordination polyelectrolytes (MEPEs). It is exceedingly difficult to characterize such macromolecular assemblies, because of the dynamic nature. Therefore, hardly any structural information is available for this type of material. Here, we show that from dilute solutions, where small aggregates predominate, it is possible to grow nanoscopic crystals at an interface. A near atomic resolution structure of MEPE is obtained by investigating the nanoscopic crystals with electron diffraction in combination with molecular model…