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Crown ether-like octanuclear molybdenum(V) clusters for cation binding and gas adsorption.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 6/7/2024, Vol. 53 Issue 21, p8980-8987, 8p
- Publication Year :
- 2024
-
Abstract
- Octanuclear polyoxomolybdenum-based porous materials, Na<subscript>8</subscript>[Mo<subscript>8</subscript>O<subscript>8</subscript>(µ<subscript>2</subscript>-O)<subscript>8</subscript>(µ<subscript>2</subscript>-OH)<subscript>8</subscript>(3-apz)<subscript>4</subscript>]<subscript>2</subscript>·26H<subscript>2</subscript>O (1, 3-Hapz = 3-aminopyrazole), K<subscript>8</subscript>[Mo<subscript>8</subscript>O<subscript>8</subscript>(µ<subscript>2</subscript>-O)<subscript>8</subscript>(µ<subscript>2</subscript>-OH)<subscript>8</subscript>(3-apz)<subscript>4</subscript>]<subscript>2</subscript>·7H<subscript>2</subscript>O (2) and (NH<subscript>4</subscript>)<subscript>4</subscript>[Mo<subscript>8</subscript>O<subscript>8</subscript>(µ<subscript>2</subscript>- O)<subscript>8</subscript>(µ<subscript>2</subscript>-OH)<subscript>4</subscript>(3-apz)<subscript>8</subscript>]·20.5H<subscript>2</subscript>O (3), have been successfully synthesized by a hydrothermal method and fully characterized. X-ray structural analyses show that microporous materials 1-3 contain round pores formed by octanuclear molybdenum-oxygen groups connected sequentially with pore sizes of 4.0, 4.0, and 4.8 Å, respectively. Both 1 and 2 are composed of two {Mo8} rings, which are connected by strong intramolecular hydrogen bonds between bridging hydroxy groups and oxygen atoms to form dimeric structures. The central pores in 1 and 2 are occupied by Na+ and K+, respectively, while they are empty in 3. This reflects the structural expansion and contraction effects induced by different cations. Through intermolecular stacking, 1-3 also exhibit channels with sizes of 14.0 × 6.4, 4.6 × 2.6, and 5.4 × 5.4 Å, respectively, which were used for the studies of gas adsorption. The results show that 1-3 can selectively adsorb CO<subscript>2</subscript> and O<subscript>2</subscript>, including the empty hole in 3, while they show little or no affinity for gases H<subscript>2</subscript>, N<subscript>2</subscript>, and CH<subscript>4</subscript>. Moreover, an additional polyoxomolybdenum-based species (Mo<subscript>8</subscript>O<subscript>26</subscript>)<subscript>n</subscript>·4n(3-H<subscript>2</subscript>apz) (4) has been obtained with protonated 3-aminopyrazole in the absence of a reducing agent, which can serve as an intermediate for the polyoxomolybdenum-based porous products. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 53
- Issue :
- 21
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 177553779
- Full Text :
- https://doi.org/10.1039/d4dt00825a