Home > Publications database > [CoxCu1x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution ‘network mismatch’ > print

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005     20190625111730.0
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024 7 _ |a 10.1039/C2DT11055E
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037 _ _ |a PreJuSER-22301
041 _ _ |a eng
082 _ _ |a 540
084 _ _ |2 WoS
|a Chemistry, Inorganic & Nuclear
100 1 _ |a Fielden, J.
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245 _ _ |a [CoxCu1x(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution ‘network mismatch’
260 _ _ |a London
|b Soc.
|c 2012
300 _ _ |a 4927 - 4934
336 7 _ |a Journal Article
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440 _ 0 |a Dalton Transactions
|x 1477-9226
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|v 411
500 _ _ |3 POF3_Assignment on 2016-02-29
500 _ _ |a 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.
520 _ _ |a 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.
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700 1 _ |a Speldrich, M.
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700 1 _ |a Kögerler, P.
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700 1 _ |a Cronin, L.
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773 _ _ |a 10.1039/c2dt11055e
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856 7 _ |u http://dx.doi.org/10.1039/C2DT11055E
856 4 _ |u https://juser.fz-juelich.de/record/22301/files/FZJ-22301.pdf
|y Published under German "Allianz" Licensing conditions on 2012-05-09. Available in OpenAccess from 2013-05-09
|z Published final document.
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