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- W3018586275 abstract "abstract In zeolite Nb,Cl,Tl-A (cubic, a = 12.120(2) A), a 3-coordinate Nb2+ ion lies opposite a 6-ring in 22% of the large cavities. In Mo,Cl,Tl-A (a = 12.110(2) A), 32% of the large cavities contain a 3-coordinate Mo+ ion at that position. A continuum of formula NbCl6Tl32+ per unit cell, consisting of octahedral NbCl6− ions linked together in three dimensions by bridging Tl+ ions, fills the large cavities and 8-ring windows in 45% of the volume (that nearest the surface) of a single crystal of Nb,Cl,Tl-A. For Mo,Cl,Tl-A, the respective formulas and values are MoCl6Tl32+, MoCl6−, and 32%. Four additional octahedral Tl+ ions per unit cell bridge between each NbCl6− or MoCl6− ion and the zeolite framework, supporting those ions at the very centers of the large cavities. Interactions with all of these Tl+ ions have lengthened all bonds in NbCl6− and MoCl6− by about 0.5 A. To prepare Nb,Cl,Tl-A, a crystal of fully dehydrated Tl-A (|Tl12|[Si12Al12O48]-A) was treated with NbCl5(g). A second such crystal was treated with MoCl5(g). The structures of the products were determined crystallographically and their compositions were confirmed by energy dispersive X-ray analysis. They were refined in the space group Pm 3 ‾ m using all data to the final error indices R1 = 0.047 for Nb,Cl,Tl-A and 0.051 for Mo,Cl,Tl-A. Both reactions failed to go to completion, presumably because the surface continua obstructed the passage of the reagent gases to the interiors of the crystals." @default.
- W3018586275 created "2020-05-01" @default.
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- W3018586275 date "2020-08-01" @default.
- W3018586275 modified "2023-09-27" @default.
- W3018586275 title "Three-coordinate extraframework Nb2+ and Mo+ in zeolite A. Crystal structures of Nb,Cl,Tl-A containing Nb2+ and NbCl6− and of Mo,Cl,Tl-A containing Mo+ and MoCl6−" @default.
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- W3018586275 doi "https://doi.org/10.1016/j.micromeso.2020.110265" @default.
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