Issue 21, 2019

Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group

Abstract

The host–guest interaction between a half spherical-type dodecavanadate (V12) and a neutral molecule guest was evaluated by monitoring the flip of a VO5 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.

Graphical abstract: Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group

Supplementary files

Article information

Article type
Paper
Submitted
31 1 2019
Accepted
03 4 2019
First published
04 4 2019

Dalton Trans., 2019,48, 7138-7143

Author version available

Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group

Y. Kikukawa, H. Kitajima and Y. Hayashi, Dalton Trans., 2019, 48, 7138 DOI: 10.1039/C9DT00462A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements