Organo-functionalized metal–oxide clusters: synthesis and characterization of the reduced cationic species [NaV^IV₆O₆{(OCH₂CH₂)₂NH}₆]⁺

Abstract

A new diethanolamine functionalized oxovanadium cationic cluster was synthesized and characterized; electrochemical and UV-vis absorption properties are consistent with two distinct MLCT processes.

Covalent Synthesis of Two Hybrids Composed of Dawson-Type Polyoxometalate and Porphyrin with Remarkable Third-Order Optical Nonlinearities Reflecting the Effect of Polyoxometalates

“…It should be mentioned that porphyrin molecules TPP-di-Tris and TPP-Tris possess two and one triol moieties, respectively. There is a substitution of three μ 2 -oxo ligands of the {V 3 } cap in the parent Dawson Polyoxometalate by the three μ 2 -alkoxy groups of the two and one triol moieties of porphyrin molecules in hybrids 1 and 2 , respectively, − and the alkoxo ligand should bridge between V centers of POMs and porphyrin molecules via sigma bonds. Besides, depending upon the configuration of amide linkage it can be deduced that the POM moiety shall direct to the opposite side in hybrid 1 , away from the porphyrin moiety due to local C 3 v symmetry, , and the conformational flexibility can afford a stable structure as a local minimum.…”

“…As it is known that fluorescence intensity strongly depends upon the molar extinction coefficient and that greater the value of extinction coefficient, the higher will be the intensity of fluorophore. TPP-di-Tris having greater molar extinction coefficient value (2.14 × 10 6 M – cm) exhibits higher fluorescence emission intensity. ,− In the case of hybrid 1 , there is more fluorescence quenching than hybrid 2 hence, there is more photo induced electron transfer from the porphyrin moieties to whole Dawson POM moiety, − leading to that quenching of porphyrin emission in hybrid 1 is more effective than in hybrid 2 .…”

Atomically precise vanadium-oxide clusters

“…8a). [118][119][120] The disparity in cluster structure between Zubieta and Khan's complexes is likely due to ligand rigidity differences, with the rigid TRIS ligands unable to accommodate the ring structure, and the ethanolamine ligands' increased flexibility favouring the less sterically confined Anderson framework. The observed tridentate binding motif arises from a VO 5 N ligand sphere, with a single terminal oxo, four bridging alkoxo, and a capping N group (Fig.…”

Organo‐Functionalized Lacunary Double Cubane‐Type Oxometallates: Synthesis, Structure, and Properties of [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (M=Co, Zn)

“…Typical IR absorption spectra of polyoxometalates contain strong bands associated with stretching modes of the terminal metal‐oxygen bond (M=O t ), and weaker bands associated with bridging oxygen (M−O b −M) vibrational modes. Band assignments are facilitated by spectral comparisons to previously studied DEA [18] and triethanolamine (TEA) [19] functionalized hexavanadate structures containing vanadium coordination octahedra like that observed in 1 and 2 . The strong band at around 958 cm −1 is attributed to the symmetric stretch of the terminal vanadium‐oxygen bond ( ν sym V=O t ).…”