Abstract

We show that a [3 + 6] trigonal prismatic imine (a) cage can rearrange stoichiometrically and structurally to form a [6 + 12] cage (b) with a truncated tetrahedral shape. Molecular simulations rationalize why this rearrangement was only observed for the prismatic [3 + 6] cage TCC1 but not for the analogous [3 + 6] cages, TCC2 and TCC3. Solvent was found to be a dominant factor in driving this rearrangement.

Highlights

  • Porous organic cages (POCs) are discrete, shape-persistent molecules that possess an intrinsic void, which is accessible via windows in the cage.[1]

  • In contrast to extended, bonded framework materials, such as metal−organic frameworks (MOFs)[2] and covalent organic frameworks (COFs),[3] POCs are often soluble in common organic solvents, opening up a number of processing options and applications.[4−6] The cage packing in the solid state has a profound effect on their properties, and this can be controlled by the size and shape of the cage, the functionality present on the outer molecular surface, and the conditions under which the cage is isolated from solvent.[7,8]

  • The ability to switch the stoichiometry of the cage products demonstrates that the energetics of host-solvent interactions can be used to fine-tune the outcome of a particular synthesis; this is similar to the amplification effect observed in dynamic combinatorial receptor libraries.[19,20]

Read more

Summary

■ INTRODUCTION

Porous organic cages (POCs) are discrete, shape-persistent molecules that possess an intrinsic void, which is accessible via windows in the cage.[1]. The precise size and shape of the resulting cage is sensitive to the choice of starting material and the position of the reactive groups with respect to one another,[7,8] and the assembly mode is not always intuitive. For this reason, we have developed computational strategies to predict the reaction outcome in silico.[12,13] For dynamic systems,[14] reversible bond formation enables error correction during synthesis and can often afford clean formation of the desired cage. Precursors and that TCC1[3+6] is able to undergo reequilibration to a larger species, TCC1[6+12], with only mild experimental stimuli (Scheme 1)

■ RESULTS AND DISCUSSION
■ ACKNOWLEDGMENTS
■ REFERENCES

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.