Lanthanide oxochalcogenido clusters.

Lanthanide chalcogenolates react with either TeO(2) in pyridine or py-SO(3) in THF to give oxychalcogenido clusters. The sulfido derivatives (THF)(8)Ln(8)S(2)O(2)(SePh)(16) (Ln = Ce, Nd) are isostructural with previously reported oxoselenido compounds, and must be prepared at low temperatures to avoid the introduction of Se into the sulfide position. Analogous telluride derivatives for the early lanthanides were not obtained, but reactions of in situ prepared Ln(TePh)(3) with elemental Te and TeO(2) gave a complicated heterocluster product, with tetrametallic polytelluride [(py)(7)Ln(4)(mu(4)-Te)(mu(2)-Te(2))(2)(mu-eta(2)-eta(2)-Te(2)Te(Ph)Te(2))(TePh)] co-crystallizing with the oxotellurido compound [(py)(5)Ln(3)(mu(3)-O)(mu(2)-Te(2))(3)(TePh)] (Ln = Ho, Er).

Lanthanide compounds with fluorinated aryloxide ligands: near-infrared emission from Nd, Tm, and Er.

Ln(OC(6)F(5))(3) form stable, isolable compounds with 1,2-dimethoxyethane (DME). Monomeric (DME)(2)Ln(OC(6)F(5))(3) (Ln = Nd, Er, Tm) adopt seven coordinate structures with two chelating DME and three terminal phenoxide ligands. Both (py)(4)Er(OC(6)F(5))(3) and (THF)(3)Yb(OC(6)F(5))(3) were also prepared and structurally characterized, with the latter being a mer-octahedral compound with bond lengths that are geometry dependent.

Lanthanide compounds with fluorinated OC6F5 ligands: homo- and heterovalent complexes of Eu(II) and Eu(III).

The fluorinated phenoxide OC6F5 forms the stable Eu(II) and Eu(III) derivatives (DME)2Eu(mu-OC6F5)3Eu(mu-OC6F5)3Eu(DME)2 and (DME)2Eu(OC6F5)3, as well as the heterovalent product (DME)2Eu(mu-OC6F5)3Eu(DME)(OC6F5)2, in redox reactions of Eu with HOC6F5 or in proton-transfer reactions of HOC6F5 with Eu(SPh)2. The divalent complex crystallizes as a trimer with three bridging phenoxides bridging each pair of metals, with the terminal metals coordinating DME and the central metal ion encapsulated totally by O(C6F5) and dative fluoride interactions. The trivalent compound is monomeric with terminal phenoxide ligands and no Eu-F interactions.

[Mo5VMo7VIO30(BPO4)2(O3P-Ph)6]5-: a phenyl-substituted molybdenum(V/VI) boro-phosphate polyoxometalate.

The title polyanion is the first hybrid borophosphate-phenylphosphonate polyoxometalate. It was structurally characterized as its imidazolium salt, (C(3)N(2)H(5))(5)[Mo(12)O(30)(BPO(4))(2)(O(3)P-Ph)(6)].H(2)O (monoclinic, P2(1)/c, a = 22.