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Issue 43, 2011
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A family of 13 tetranuclear zinc(ii)-lanthanide(iii) complexes of a [3 + 3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

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Abstract

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (LPr)6−, with general formula ZnII3LnIII(LPr)(NO3)3·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3 : 1 : 3 : 3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H2L1) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn6(LPr)(OAc)5(OH)(H2O)]·3H2O was obtained using a 2 : 0 : 1 : 1 ratio of the same reagents. A control experiment using a 1 : 0 : 1 : 1 ratio failed to generate the lanthanide-free [Zn3(LPr)] macrocyclic complex. The reaction of H2L1 and zinc(II) acetate in a 1 : 1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H2L1, [Zn5(L1)5(H2O)6]·3H2O. An X-ray crystal structure determination revealed [Zn3IIPrIII(LPr)(NO3)2(DMF)3](NO3)·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O6 site with two bidentate nitrate anions completing the O10 coordination sphere. The three square pyramidal zinc(II) ions are in the outer N2O2 sites with a fifth donor from DMF. Measurement of the magnetic properties of [ZnII3DyIII(LPr)(NO3)3(MeOH)3]·4H2O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution.

Graphical abstract: A family of 13 tetranuclear zinc(ii)-lanthanide(iii) complexes of a [3 + 3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

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Supplementary files

Article information


Submitted
03 Jun 2011
Accepted
11 Aug 2011
First published
21 Sep 2011

Dalton Trans., 2011,40, 11425-11432
Article type
Paper

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3 + 3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

H. L. C. Feltham, F. Klöwer, S. A. Cameron, D. S. Larsen, Y. Lan, M. Tropiano, S. Faulkner, A. K. Powell and S. Brooker, Dalton Trans., 2011, 40, 11425
DOI: 10.1039/C1DT11038A

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