Wydział Chemii

Jinhua Wang

Liat Avram

Yael Diskin-Posner

Michał J. Białek

Wojciech Stawski

Moran Feller

Rafal Klajn

2022

Journal of the American Chemical Society

144

21244-21254

10.1021/jacs.2c08901

Naukowa

Angielski

Artykuł

Molecular confinement effects can profoundly alter the physicochemical properties of the confined species. A plethora of organic molecules were encapsulated within the cavities of supramolecular hosts, and the impact of the cavity size and polarity was widely investigated. However, the extent to which the properties of the confined guests can be affected by the symmetry of the cage─which dictates the shape of the cavity─remains to be understood. Here we show that cage symmetry has a dramatic effect on the equilibrium between two isomers of the encapsulated spiropyran guests. Working with two Pd-based coordination cages featuring similarly sized but differently shaped hydrophobic cavities, we found a highly selective stabilization of the isomer whose shape matches that of the cavity of the cage. A T_d-symmetric cage stabilized the spiropyrans’ colorless form and rendered them photochemically inert. In contrast, a D_2h-symmetric cage favored the colored isomer, while maintaining reversible photoswitching between the two states of the encapsulated spiropyrans. We also show that the switching kinetics strongly depend on the substitution pattern on the spiropyran scaffold. This finding was used to fabricate a time-sensitive information storage medium with tunable lifetimes of the encoded messages.

Cavities, Encapsulation, Light, Molecular structure, Nuclear magnetic resonance spectroscopy

CC-BY

http://dx.doi.org/10.1021/jacs.2c08901

https://www.acs.org/content/acs/en.html