The reaction of aqueous [W
3S
7(C
2O
4)
3]
2- with Ln
3+ and Th
4+ in a 1:1 molar ratio leads to oxalate-bridgedheteropolynuclear molecular complexes and coordination polymers. La
3+ and Ce
3+ give a layered structure with big(about 1.8 nm) honeycomb pores which are filled with water molecules and lanthanide ions, in {[Ln(H
2O)
6]
3[W
3S
7(C
2O
4)
3]
4}Br·
xH
2O (
Ia and
Ib). The smaller Pr
3+, Nd
3+, Sm
3+, Eu
3+, and Gd
3+ ions give discrete nanomolecules[(W
3S
7(C
2O
4)
3Ln(H
2O)
5)
2(
-C
2O
4)] (with a separation of about 3.2 nm between the most distant parts of the molecule),which are further united into zigzag chains by specific S
2···Br
- contacts to achieve the overall stoichiometry K[(W
3S
7(C
2O
4)
3Ln(H
2O)
5)
2(
-C
2O
4)]Br·
xH
2O (
IIa-
IId). Th
4+ gives K
2[(W
3S
7(C
2O
4)
3)
4Th
2(OH)
2(H
2O)
10]·14.33H
2O (
III) with ananosized discrete anion (with a separation of about 2.7 nm between the most distant parts of the molecule), inwhich two thorium atoms are bound via two hydroxide groups into the Th
2(OH)
26+ unit, and each Th is furthercoordinated by five water molecules and two monodentate [W
3S
7(C
2O
4)]
2- cluster ligands. All compounds werecharacterized by X-ray structure analysis and IR spectroscopy. Magnetic susceptibility measurements in thetemperature range of 2-300 K show weak antiferromagnetic interactions between two lanthanides atoms forcompounds
IIa,
IIb, and
IId. The thermal decomposition of
Ia,
Ib, and
IIb was studied by thermogravimetry.
