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

Jack K. Clegg, Michael J. Hayter, Katrina A. Jolliffe, Leonard F. Lindoy, John C. McMurtrie, George V. Meehan, Suzanne M. Neville, Simon Parsons, Peter A. Tasker, Peter Turner, Fraser J. White

Research output: Contribution to journalArticlepeer-review

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-beta-diketones of type [RC(=O)CH2C(=O)C6H4C(=O)CH2C-(=O)R] ((LH2)-H-1) 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 [Cu-2(L-1)2]center dot 2.5THF (R = Me), [Cu-2(L-1)(2)(THF)(2)] (R = t-Bu), [Ni-2(L-1)(2)(Py)(4)] (R = t-Bu) and [Co-2(L-1)(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: [Cu-2(L-1)(2)(Py)(2)]center dot Py (R = Me), [Cu-2(L-1)(2)(EtPy)(2)]center dot 2EtPy (R = t-Bu), [Cu-2(L-1)(2)(pipi)(2)]center dot 2pipi (R = t-Bu), [Cu-2(L-1)(2)(mmorph)(2)] (R= t-Bu), [Cu-2(L-1)(2)(tmen)(2)] (R= t-Bu) and {[Cu-2(L-1)(2)(pip)]center dot pip center dot 2THF}(n), [Co-2(L-1)(2)(tmen)(2)] (R = t-Bu), [Ni-2(L-1)(2)(Py)(4)]center dot dmpip (R = t-Bu), [Ni-2(L-1)(2)(pipi)(4)]center dot pipi (R = t-Bu) and [Ni-2(L-1)(2)(tmen)(2)] (R = t-Bu). The effect of pressure on the X-ray structure of [Cu-2(L-1)(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.

Original languageEnglish
Pages (from-to)2804-2815
Number of pages12
JournalDalton Transactions
Volume39
Issue number11
DOIs
Publication statusPublished - 2010

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