A New Family of Polyoxometalates: Tris-functionalized Lindqvist-Type Hexatungstovanadates

Abstract

We successfully designed and obtained a new family of polyoxometalates (POMs) containing mixed-metal elements and a trialkoxyl (TRIS) ligand via a very simple one-pot process under mild condition. Single-crystal X-ray diffraction revealed that this family belongs to compact Lindqvist-type hexatungstovanadates. In particular, the hydroxyl-containing product can be further functionalized through esterification. Not only does this work open a broad door for unusual POM clusters involving vanadium and tungsten atoms in the future, but also the design concept of this work also provides new insight for the synthesis and further exploration of POMs.

Electrochemical and Structural Characterization of Soft Landed Tungsten‐Substituted Lindqvist Polyoxovanadate‐Alkoxides

“…A previous study of soft‐landed W‐POM shows the W=O t band at 981 cm −1 , which is close in value to the M=O t bands seen in Figure 3B [57] . In the IRRAS spectrum of WV 5 a new band is observed at 817 cm −1 (Figure 3B), which is assigned as the asymmetric O−W‐O stretching mode that is typically observed in infrared spectra of tungsten oxides at ∼820 cm −1 [16,48,58–60] . We also observe that the M=O t band splits into at least two peaks in the spectrum of WV 5 in Figure 3B.…”

“…[57] In the IRRAS spectrum of WV 5 a new band is observed at 817 cm À 1 (Figure 3B), which is assigned as the asymmetric OÀ W-O stretching mode that is typically observed in infrared spectra of tungsten oxides at ~820 cm À 1 . [16,48,[58][59][60] We also observe that the M=O t band splits into at least two peaks in the spectrum of WV 5 in Figure 3B. Similarly, the O b À CH 3 stretching band shifts and broadens as tungsten is substituted into the core.…”

“…The spectrum of V 6 is dominated by a singly charged peak at m/z 789.849; the isotopic pattern observed for this anion shown in the insert is consistent with the calculated isotopic pattern of V 6 . In comparison, the spectrum of the ) and its tris-alkoxide (TRIOL R )bridged analogue [14][15][16][17][18][19] (top), as well as the W-substituted POV-alkoxides WV 5 and W 2 V 4 reported in this work (bottom).…”

“… Schematic representations of previously reported Lindqvist polyoxovanadate‐alkoxide clusters V 6 O 7 (OCH 3 ) 12 ( V 6 ) and its tris‐alkoxide (TRIOL R )‐bridged analogue [14–19] (top), as well as the W‐substituted POV‐alkoxides WV 5 and W 2 V 4 reported in this work (bottom).…”

Computationally assisted design and prediction of remarkably boosted NLO response of organoimido‐substituted hexamolybdates

“…In the present years, the organoimido-based POMs have been comprehensively explored, and main concern has given to hexamolybdate ion, [Mo 6 O 19 ] 2which usually possesses Lindquist structure. [10] The Lindquist structure has six oxygens; that is, one oxygen at each terminal position and each oxygen atom can be changed by an organic part to build hybrid materials. [11][12][13][14][15][16][17][18][19][20][21][22][23] Direct functionalization of POM cluster of hexamolybdates was done by Maatta et al [15] several years ago which facilitated to perform the further functionalization of POM cages.…”