Construction of Mesoporous Frameworks with Vanadoborate Clusters

Chen, Hong; Yu, Zheng-Bao; Bacsik, Zoltán; Zhao, Huichang; Yao, Qingxia; Sun, Junliang

doi:10.1002/anie.201311122

Cited by 56 publications

(53 citation statements)

References 42 publications

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“…52 Bond valence summation showed that vanadium has an average bond valence sum of approximately +4.2018 without any preferential occupancies for V 4+ and V 5+ in SUT-10, consistent with its dark green color. 40 This result was further confirmed by the XPS results with a peak at 516.3 eV with a shoulder beside, corresponding to V 4+ 2p 3/2 and V 5+ 2p 3/2 ( Figure S4). 41 Different from that of SUT-10, the bond valence summation for vanadium in SUT-11 clusters is +4.05, indicated by the slightly longer bond lengths and light green color ( Figure S6).…”

Section: Inorganic Chemistrysupporting

confidence: 68%

Construct Polyoxometalate Frameworks through Covalent Bonds

Chen

Zhao

et al. 2015

Inorg. Chem.

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An emerging strategy for exploring the application of polyoxometalates (POMs) is to assemble POM clusters into open-framework materials, especially inorganic-organic hybrid three-dimensional (3D) open-framework materials, via the introduction of different organic linkers between the POM clusters. This strategy has yielded a few 3D crystalline POMs of which a typical class is the group of polyoxometalate metal-organic frameworks (POMMOFs). However, for reported POMMOFs, only coordination bonds are involved between the linkers and POM clusters, and it has not yet produced any covalently bonded polyoxometalate frameworks. Here, the concept of "covalently bonded POMs (CPOMs)" is developed. By using vanadoborates as an example, we showed that the 3D CPOMs can be obtained by a condensation reaction through the oxolation mechanism of polymer chemistry. In particular, suitable single crystals were harvested and characterized by single-crystal X-ray diffraction. This work forges a link among polymer science, POM chemistry, and open-framework materials by demonstrating that it is possible to use covalent bonds according to polymer chemistry principles to construct crystalline 3D open-framework POM materials.

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Section: Inorganic Chemistrysupporting

confidence: 68%

Construct Polyoxometalate Frameworks through Covalent Bonds

Chen

Zhao

et al. 2015

Inorg. Chem.

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“…2 The scope of such 25 frameworks is no longer limited to metal phosphates (such as aluminosilicate zeolites, aluminophosphates, zincophosphates and gallium phosphates), but instead to mainly include metal borates and their derivatives (such as metal borophosphates, 3 borogermanates 4 and borovanadates 5, 6 ). Resulting from the 75 structure with nonlinear optical properties. 9 (iii) V IVcontaining compounds have caused great interest owing to their inherent magnetism.…”

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confidence: 99%

A new 3-D open-framework cadmium borovanadate with plane-shaped channels and high catalytic activity for the oxidation of cyclohexanol

Feng

Qiu

et al. 2015

Dalton Trans.

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“…The known vanadoborates have now been classified into the following four categories [24]:V 6 B 20 species containing a V 6 macrohexagon imbedded in a B 20 borate matrix, typically corresponding to a [V 6 B 20 O 50 H 8 ] 8− anion building block [2,3,25]. …”

Section: The High-spin Vanadoborate Analogue Of Benzenementioning

confidence: 99%

Analogies between Vanadoborates and Planar Aromatic Hydrocarbons: A High-Spin Analogue of Aromaticity

King

2017

Materials

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The vanadium-vanadium interactions in the polygonal aggregates of d1 vanadium(IV) atoms, with a total of 4k + 2 vanadium electrons (k an integer) imbedded in an electronically inactive borate matrix in certain vanadoborate structures are analogous to the ring carbon-carbon interactions in diamagnetic planar cyclic hydrocarbons. They thus represent a high-spin analogue of aromaticity. Thus, the vanadoborate anion [V6B20O50H8]8− with six V(IV) electrons (i.e., 4k + 2 for k = 1) contains a macrohexagon of d1 V(IV) atoms with four unpaired electrons. This high-spin system is related to the low-spin aromaticity in the diamagnetic benzene having six π electrons. Similarly, the vanadoborate anion [V10B28O74H8]16− with ten V(IV) electrons (i.e., 4k + 2 for k = 2) contains a macrodecagon of d1 V(IV) atoms with eight unpaired electrons. Again, this high-spin system is related to the aromaticity in the diamagnetic 1,6-methanol[10]annulene, having ten π electrons.

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Construction of Mesoporous Frameworks with Vanadoborate Clusters

Cited by 56 publications

References 42 publications

Construct Polyoxometalate Frameworks through Covalent Bonds

Construct Polyoxometalate Frameworks through Covalent Bonds

A new 3-D open-framework cadmium borovanadate with plane-shaped channels and high catalytic activity for the oxidation of cyclohexanol

Analogies between Vanadoborates and Planar Aromatic Hydrocarbons: A High-Spin Analogue of Aromaticity

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