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.