Coaggregation of paramagnetic d- and f-block metal ions with a podand-framework amine phenol ligand.
This report covers initial studies in the coaggregation of nickel (Ni2+) and lanthanide (Ln3+) metal ions to form complexes with interesting structural and magnetic properties. The tripodal amine phenol ligand H3tam (1,1,1-tris(((2-hydroxybenzyl)amino)methyl)ethane) is shown to be particularly accommodating with respect to the geometric constraints of both transition and lanthanide metal ions, forming isolable complexes with both of these ion types. In the solid-state structure of [Ni(H2tam)(CH3CN)]PF6.2.5CH3CN.0.5CH3OH (1), the Ni(II) center has a distorted octahedral geometry, with an N3O2 donor set from the [H2tam]- ligand and a coordinated solvent (acetonitrile) occupying the sixth site. The reaction of stoichiometric amounts of H3tam with the Ni(II) ion in the presence of lanthanide(III) ions provides [LnNi2(tam)2]+ cationic complexes which contain coaggregated metal ions. These complexes are isolable and have been characterized by a variety of analytical techniques, with mass spectrometry proving to be particularly diagnostic. The solid-state structures of [LaNi2(tam)2(CH3OH)1/2(CH3CH2OH)1/2(H2O)]ClO4.0.5CH3OH.0.5CH3CH2OH.4H2O (2), [DyNi2(tam)2(CH3OH)(H2O)]ClO4.CH3OH. H2O(6), and [YbNi2(tam)2(H2O)]ClO4.2.58H2O(9) have been determined. Each complex contains two octahedral Ni(II) ions, each of which is encapsulated by the ligand tam3- in an N3O3 coordination sphere; each [Ni(tam)]-unit caps the lanthanide(III) ion via bridging phenoxy oxygen donor atoms. In 2, La3+ is eight-coordinated, while in 6, Dy(III) is seven- (to "weakly eight-") coordinated, and Yb(III) in 9 has a six-coordination environment. The complexes are symmetrically different, 2 possessing C2 symmetry and 6 and 9 having C1 symmetry. Magnetic studies of 2, 6, and 9 indicate that antiferromagnetic exchange coupling between the Ni(II) and Ln(III) ions increases with decreasing ionic radius of Ln(III).
Department of Chemistry, University of British Columbia, Vancouver, Canada.
Z
Z
Xu
P W
PW
Read
D E
DE
Hibbs
M B
MB
Hursthouse
K M
KM
Abdul Malik
B O
BO
Patrick
S J
SJ
Rettig
M
M
Seid
D A
DA
Summers
M
M
Pink
R C
RC
Thompson
C
C
Orvig
D000588:Amines / Q000737:chemistry; D003287:Contrast Media / Q000737:chemistry; D008024:Ligands; D008280:Magnetics; D008674:Metals, Rare Earth / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010636:Phenols / Q000737:chemistry
D000588:Amines; D003287:Contrast Media; D008024:Ligands; D008674:Metals, Rare Earth; D009942:Organometallic Compounds; D010636:Phenols; D009532:Nickel