Details

Autor(en) / Beteiligte

• Beyer, Andreas
• von Gernler, Marc S.
• Pflock, Stephan
• Türkoglu, Gazi
• Müller, Lisa
• Zahl, Achim
• Gieb, Klaus
• Müller, Paul
• Drewello, Thomas
• Burzlaff, Nicolai

Titel

Alkali‐Metal‐Templated Self‐Assembly of Nickel(II) [12‐MC‐3] Metallacoronates Based on Bis(pyrazol‐1‐yl)acetato Ligands

Ist Teil von

• European journal of inorganic chemistry, 2018-02, Vol.2018 (6), p.765-777

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2018

Link zum Volltext

Quelle

Wiley Blackwell Single Titles

Beschreibungen/Notizen

• The syntheses and structures of four new bis(pyrazol‐1‐yl)acetate‐ or bis(3,5‐dimethylpyrazol‐1‐yl)acetate‐based bis‐ligand nickel(II) complexes [Ni(bdmpzmp)2] (1), [Ni(bdmpzpen)2] (2), [Ni(bdmpza)2] (3), and [Ni(bpza)2] (4) are described. The results of single crystal structure determinations reveal for all four complexes κ3‐coordination of the scorpionate ligands. The sterically hindered bis(3,5‐di‐tert‐butyl‐pyrazol‐1‐yl)acetateto (bdtbpza) ligand allows the synthesis of the nickel(II) chlorido complex [Ni(bdtbpza)Cl] (5). Furthermore, controlled formation of a novel trinuclear linear complex [Ni(bdmpza)2{Ni(acac)(bdmpza)}2] (6) [bdmpza = bis(3,5‐dimethylpyrazol‐1‐yl)acetate] by a self‐assembling reaction and alkali metal‐mediated template syntheses of [Na{Ni(acac)(bdmpza)}3]NO3 (7), [Na{Ni(acac)(bdmpza)}3]I (8) and [Li{Ni(acac)(bdmpza)}3]NO3 (9) are reported. ESI MS allowed a detailed characterization in solution and is supported by X‐ray structure analysis. Compounds 7, 8 and 9 exhibit [12‐MC‐3] metallacrown structures with a sixfold coordinated alkali metal ion in the center. The magnetic properties are studied by SQUID. Crystallographic data reveal broken symmetry in the solid state for all three [12‐MC‐3] metallacoronates 7, 8 and 9. The linear structure of [Ni(bdmpza)2{Ni(acac)(bdmpza)}2] (6) (length ≈ 2 nm) obtained through synthesis without template, as well as the molecular structure of the [12‐MC‐3] metallacoronates 7, 8 and 9 (∅ ≈ 1.3 nm) are at the nanoscale. Trinuclear nickel(II) complexes based on the bis(3,5‐dimethylpyrazol‐1‐yl)acetato and the acac ligand are formed by self‐assembling reactions. Controlled by alkali metal ions as templates either linear complexes or [12‐MC‐3] metallacrown/metallcoronate structures are formed.