Journal Article

PreJuSER-22301

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png [CoxCu1x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution ‘network mismatch’

Fielden, J. ; Long, D.-L. ; Speldrich, M. ; Kögerler, P.FZJ* ; Cronin, L.

2012
Soc. London

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Please use a persistent id in citations: http://hdl.handle.net/2128/7524  doi:10.1039/C2DT11055E

Abstract: Late-first row transition metal nitrate complexes of the tetradentate N-donor ligand cis-3,5-bis[(2-pyridinyleneamino]-trans-hydroxycyclohexane (DDOP) adopt a mono-cationic [M(DDOP)(H(2)O)(NO(3))](+) structure (M = Co, 1; Cu, 2; Zn, 3) in which the DDOP ligand occupies the equatorial plane. The complexes are essentially isostructural and isomorphous, allowing the Co(II) and Cu(II) complexes to co-crystallize in mixed-metal solid solutions with the formula [Co(x)Cu(1-x)(DDOP)(NO(3))(H(2)O)](NO(3)), where x = 0.4 (4), 0.1 (5), and 0.7 (6). For 4, structural and magnetochemical analysis indicate that the geometry of the octahedral Co(II) complex distorts to match that of the dominant Jahn-Teller distorted Cu(II) center. Magnetic susceptibility data of octahedral Co(II) are sensitive to ligand geometry distortions and have been analyzed accordingly, comparing 4 to the reference systems 1 and 2. Bond valence calculations have been used to estimate the relative stabilities of the six hydrogen bonded networks, suggesting that the stretching of the Co(II) coordination sphere 4 in is assisted by adoption of the most stable hydrogen bonded network; but that in 6 this is overcome by a higher loading of Co. This family of complexes therefore represent predictable metal-based tectons which can help probe the influence of secondary non-covalent interactions over metal coordination geometries and properties.

Keyword(s): J

Note: We thank Claire Besson for suggesting use of the bond-valence method, Georg Seeber for X-ray diffraction data for compound 2, Kevin Lamberts for X-ray diffraction data on the additional solid solutions (ESI) and Geoff Cooper for re-synthesis of 4. JF and DL both acknowledge the EPSRC for funding.

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Contributing Institute(s):

1. Elektronische Eigenschaften (PGI-6)

Research Program(s):

1. Grundlagen für zukünftige Informationstechnologien (P42)

Appears in the scientific report 2012

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Database coverage:
; ; Allianz-Lizenz / DFG ; Current Contents - Social and Behavioral Sciences ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

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