Early‐Lanthanide Complexes with All‐Inorganic Macrocyclic Polyoxovanadate Ligands

Abstract

Keywords: Polyoxometalates / Vanadates / Lanthanides / Inorganic ligandsThree discrete early-lanthanide complexes with cyclic polyoxovanadate ligands, [LaV 10 O 30 ] 7-(1), [CeV 9 O 27 ] 6-(2), and [PrV 9 O 27 ] 6- (3), were synthesized by reaction of [VO 3 ]with early-lanthanide(III) salts. Complexes 1-3 were composed of a Ln III center in square-antiprism coordination mode with coordinated all-inorganic ligands [V n O 3n ] n-(n = 9 or 10), which were constructed from a cyclic linkage of nine or ten VO 4 tetrahedra through vertex sharing. Structural investigation of lanthanum complex 1 revealed a ten-membered ring of VO 4 units in which eight VO 4 units were coordinated to the lanthanum atom through their oxido groups and two VO 4 units [a]

Yttrium‐Containing Sandwich‐, Ring‐, and Cage‐Type Polyoxovanadates: Synthesis and Characterization

“…[8] To synthesize 2, 1 is dissolved in a mixed solvent of water and acetonitrile (1:99 v/v), and then {Et 4 N}[VO 3 ] (1 equiv.) Although the crystal-structure analysis of 2 was unsuccessful, the IR spectrum clearly indicates the structural identity of 2, because the IR spectroscopic pattern in the fingerprint region matches exactly that of the previously reported complexes, [RE(V 9 O 27 )] 6-{RE = Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , and Dy 3+ } [6,7] (Figure 3, Figure S7). Although the crystal-structure analysis of 2 was unsuccessful, the IR spectrum clearly indicates the structural identity of 2, because the IR spectroscopic pattern in the fingerprint region matches exactly that of the previously reported complexes, [RE(V 9 O 27 )] 6-{RE = Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , and Dy 3+ } [6,7] (Figure 3, Figure S7).…”

“…Although the crystal-structure analysis of 2 was unsuccessful, the IR spectrum clearly indicates the structural identity of 2, because the IR spectroscopic pattern in the fingerprint region matches exactly that of the previously reported complexes, [RE(V 9 O 27 )] 6-{RE = Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , and Dy 3+ } [6,7] (Figure 3, Figure S7). [7] (Bottom) IR spectra of: (a) previously reported [Ce(V 9 O 27 )] 6in ref. [7] (Bottom) IR spectra of: (a) previously reported [Ce(V 9 O 27 )] 6in ref.…”

“…[6] The IR spectra of 1 and the holmium-containing polyoxovanadate show almost identical spectra in the fingerprint region of the polyoxovanadate frameworks (1100-400 cm -1 ) ( Figure S1). ), the peak due to {(Et 4 N) 6 [YV 8 O 24 ]} + decreases and the relative intensity of the peak due to {(Et 4 N) 7 From these results, the isolation of yttrium-containing polyoxovanadates in the presence of additives has been investigated. The formation of 1 is expressed by Equation (1): To confirm the solution-state stability, crystals of 1 were dissolved in acetonitrile and the CSI-MS was recorded.…”

“…Compound 3 possesses a cubane-type tetranuclear yttrium core, [Y 4 (OH) 4 ] 8+ , wrapped by a polyoxovanadate framework. The structures of mononuclear rare-earthmetal-containing polyoxovanadates are divided into four types, according to the formulae: [REV 10 [6,7] These adopted structures correlate with the ionic radii of the rare-earth-metal cations. The vanadate framework of 3 consists of condensed [V 11 O 33 ] 11rings sharing three-coordinate VO 4 units as a bridgehead, as in an adamantane framework.…”

Structural conversion from bowl- to ball-type polyoxovanadates: Synthesis of a spherical tetradecavanadate through a chloride-incorporated bowl-type dodecavanadate

“…Inorganic complexes between a crown-type polyoxovanadate, (VO 3 ) n n-, and a transition metal cation produced a type of inorganic coordination complexes with a vanadium ring size of 4 < n < 10, depending on the type of metal cation used as a template [27][28][29][30]. To elucidate the reactivity of all-inorganic coordination complexes, a template-removal reaction was developed using the copper complex, …”