Issue 11, 2010

New discrete and polymeric supramolecular architectures derived from dinuclear Co(ii), Ni(ii) and Cu(ii) complexes of aryl-linked bis-β-diketonato ligands and nitrogen bases: synthetic, structural and high pressure studies

Abstract

New examples of nitrogen base adducts of dinuclear Co(II), Ni(II) and Cu(II) complexes of the doubly deprotonated forms of 1,3-aryl linked bis-β-diketones of type [RC([double bond, length as m-dash]O)CH2C([double bond, length as m-dash]O)C6H4C([double bond, length as m-dash]O)CH2C([double bond, length as m-dash]O)R] (L1H2) incorporating the mono- and difunctional amine bases pyridine (Py), 4-ethylpyridine (EtPy), piperidine (pipi), 1,4-piperazine (pip), N-methylmorpholine (mmorph), 1,4-dimethylpiperazine (dmpip) and N,N,N′,N′-tetramethylethylenediamine (tmen) have been synthesised by reaction of the previously reported [Cu2(L1)2]·2.5THF (R = Me), [Cu2(L1)2(THF)2] (R = t-Bu), [Ni2(L1)2(Py)4] (R = t-Bu) and [Co2(L1)2(Py)4] (R = t-Bu) complexes with individual bases of the above type. Comparative X-ray structural studies involving all ten base adduct derivatives have been obtained and reveal a range of interesting discrete and polymeric molecular architectures. The respective products have the following stoichiometries: [Cu2(L1)2(Py)2]·Py (R = Me), [Cu2(L1)2(EtPy)2]·2EtPy (R = t-Bu), [Cu2(L1)2(pipi)2]·2pipi (R = t-Bu), [Cu2(L1)2(mmorph)2] (R = t-Bu), [Cu2(L1)2(tmen)2] (R = t-Bu) and {[Cu2(L1)2(pip)]·pip·2THF}n, [Co2(L1)2(tmen)2] (R = t-Bu), [Ni2(L1)2(Py)4]·dmpip (R = t-Bu), [Ni2(L1)2(pipi)4]·pipi (R = t-Bu) and [Ni2(L1)2(tmen)2] (R = t-Bu). The effect of pressure on the X-ray structure of [Cu2(L1)2(mmorph)2] has been investigated. An increase in pressure from ambient to 9.1 kbar resulted in modest changes to the unit cell parameters as well as a corresponding decrease of 6.7 percent in the unit cell volume. While a small ‘shearing’ motion occurs between adjacent molecular units throughout the lattice, no existing bonds are broken or new bonds formed.

Graphical abstract: New discrete and polymeric supramolecular architectures derived from dinuclear Co(ii), Ni(ii) and Cu(ii) complexes of aryl-linked bis-β-diketonato ligands and nitrogen bases: synthetic, structural and high pressure studies

Supplementary files

Article information

Article type
Paper
Submitted
29 Sep 2009
Accepted
04 Dec 2009
First published
02 Feb 2010

Dalton Trans., 2010,39, 2804-2815

New discrete and polymeric supramolecular architectures derived from dinuclear Co(II), Ni(II) and Cu(II) complexes of aryl-linked bis-β-diketonato ligands and nitrogen bases: synthetic, structural and high pressure studies

J. K. Clegg, M. J. Hayter, K. A. Jolliffe, L. F. Lindoy, J. C. McMurtrie, G. V. Meehan, S. M. Neville, S. Parsons, P. A. Tasker, P. Turner and F. J. White, Dalton Trans., 2010, 39, 2804 DOI: 10.1039/B920199H

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