Crown ether-like discrete clusters for sodium binding and gas adsorption
Hexanuclear polyoxomolybdenum-based discrete supermolecules Na x [Mo V 6 O 6 (μ 2 -O) 9 (Htrz) 6− x (trz) x ]· n H 2 O ( x = 0, n = 15, 1 ; x = 1, n = 12, 2 ; x = 2, n = 10, 3 ; x = 2, n = 49, 4 ; Htrz = 1 H -1,2,3-triazole) have been prepared and fully characterized with different amounts of sodium...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 52; no. 25; pp. 88 - 881 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
27.06.2023
|
| Subjects | |
| Online Access | Get full text |
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| Summary: | Hexanuclear polyoxomolybdenum-based discrete supermolecules Na
x
[Mo
V
6
O
6
(μ
2
-O)
9
(Htrz)
6−
x
(trz)
x
]·
n
H
2
O (
x
= 0,
n
= 15,
1
;
x
= 1,
n
= 12,
2
;
x
= 2,
n
= 10,
3
;
x
= 2,
n
= 49,
4
; Htrz = 1
H
-1,2,3-triazole) have been prepared and fully characterized with different amounts of sodium cations inside and outside the intrinsic holes. Structural analyses demonstrate that they all exist a triangular channel constructed by six molybdenum-oxygen groups with inner diameters of 2.86 (
1
), 2.48 (
2
), and 3.04 (
3
/
4
) Å, respectively. Zero, one, or two univalent enthetic guest Na
+
have been hosted around the structural centers, which reflect the expansion and contraction effects at microscopic level. Water-soluble species can serve as crown ether-like metallacycles before and after the sodium binding. Diverse nanoscale pores are further formed through intermolecular accumulations with hydrogen bonding. Gas adsorption studies indicate that
2-4
can selectively adsorb CO
2
and O
2
but have little or even no affinities toward H
2
, N
2
, and CH
4
. Theoretical calculations corroborate the roles of Na
+
and auxiliary ligand with different states in bond distances, molecular orbitals, electrostatic potentials, and lattice energies in these discrete clusters. The binding orders of sodium cations in
2-4
are similar with the classical crown ethers, where
2
is the strongest one with 2.226(4)
av
Å for sodium cation bonded to six O atoms.
Hexanuclear molybdenum-based discrete clusters can be regarded as crown ether-like metallacycles. The embedding of different amounts of Na
+
results in different sizes of the intrinsic holes. Theoretical calculations give the binding order influenced by Na
+
/triazole
−
. |
|---|---|
| Bibliography: | CCDC crystallographic details, selected bond distances and angles, hydrogen bonds, comparisons of bond distances, bond valence calculations for molybdenum in 13 1-1-4-1 C NMR spectrum for 1 H adsorption isotherms and data for geometry optimized coordinates for compounds CO and CH N pore distributions, optimized individual conformers and calculated frontier molecular orbitals and energies in For ESI and crystallographic data in CIF or other electronic format see DOI 2 Electronic supplementary information (ESI) available: Perspective views, packing diagrams, topological nets, IR and solid UV-vis spectra, TG curves, powder XRD curves, EPR spectra, solution 2232987-2232990 adsorption-desorption isotherms, O 4 and selected bond lengths and NPA charges in 1-4 1,2,3-triazole, N 2-4 https://doi.org/10.1039/d3dt00341h ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 |
| ISSN: | 1477-9226 1477-9234 1477-9234 |
| DOI: | 10.1039/d3dt00341h |