Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group
The host-guest interaction between a half spherical-type dodecavanadate ( V12 ) and a neutral molecule guest was evaluated by monitoring the flip of a VO 5 unit caused by the presence or absence of a guest in the cavity of V12 . In N , N -dimethylformamide (DMF), V12 adopted the guest-free form ( V1...
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Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 48; no. 21; pp. 7138 - 7143 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
England
07.06.2019
|
Online Access | Get full text |
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Summary: | The host-guest interaction between a half spherical-type dodecavanadate (
V12
) and a neutral molecule guest was evaluated by monitoring the flip of a VO
5
unit caused by the presence or absence of a guest in the cavity of
V12
. In
N
,
N
-dimethylformamide (DMF),
V12
adopted the guest-free form (
V12-free
). By the addition of several guest molecules, such as acetonitrile, nitromethane, and dichloromethane, the structural conversion to the guest-inserted form (
V12(guest)
) was observed with the affinity constants of 137 ± 10 M
−1
, 0.14 ± 0.1 M
−1
, and 0.15 ± 0.1 M
−1
, respectively. In the case of 1,2-dichloroethane, 1,2-dibromoethane, and 1,2-diiodoethane, the constants were 35 ± 5 M
−1
, 114 ± 5 M
−1
, and 2.1 ± 0.5 M
−1
, respectively, suggesting that the bromo group is the best fit to the cavity of the bowl. A cyclic carbonate, 5- and 6-membered lactones, cyclobutanone, and hexanal were inserted into the
V12
host, while a non-cyclic carbonate, non-cyclic and 7-membered cyclic ester, a ketone with a 5-membered ring, and benzaldehyde showed no effect on the guest insertion. The
V12
host preferred to hold a guest with an electron-rich group, and the bowl-type structure showed the unique shape-selective interaction with the guest.
The affinity between a guest molecule and a dodecavanadate host molecule was evaluated
via
monitoring the structural transformation caused by the presence of a guest molecule. |
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Bibliography: | 10.1039/c9dt00462a Electronic supplementary information (ESI) available. See DOI ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c9dt00462a |