TetrazineBox: A Structurally Transformative Toolbox

Qing Hui Guo, Jiawang Zhou, Haochuan Mao, Yunyan Qiu, Minh T. Nguyen, Yuanning Feng, Jiaqi Liang, Dengke Shen, Penghao Li, Zhichang Liu, Michael R. Wasielewski, J. Fraser Stoddart

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Synthetic macrocycles capable of undergoing allosteric regulation by responding to versatile external stimuli are the subject of increasing attention in supramolecular science. Herein, we report a structurally transformative tetracationic cyclophane containing two 3,6-bis(4-pyridyl)-l,2,4,5-tetrazine (4-bptz) units, which are linked together by two p-xylylene bridges. The cyclophane, which possesses modular redox states and structural post-modifications, can undergo two reversibly consecutive two-electron reductions, affording first its bisradical dicationic counterpart, and then subsequently the fully reduced species. Furthermore, one single-parent cyclophane can afford effectively three other new analogs through box-to-box cascade transformations, taking advantage of either reductions or an inverse electron-demand Diels-Alder (IEDDA) reaction. While all four new tetracationic cyclophanes adopt rigid and symmetric box-like conformations, their geometries in relation to size, shape, electronic properties, and binding affinities toward polycyclic aromatic hydrocarbons can be readily regulated. This structurally transformative tetracationic cyclophane performs a variety of new tasks as a result of structural post-modifications, thus serving as a toolbox for probing the radical properties and generating rapidly a range of structurally diverse cyclophanes by efficient divergent syntheses. This research lays a solid foundation for the introduction of the structurally transformative tetracationic cyclophane into the realm of mechanically interlocked molecules and will provide a toolbox to construct and operate intelligent molecular machines.

Original languageEnglish
Pages (from-to)5419-5428
Number of pages10
JournalJournal of the American Chemical Society
Volume142
Issue number11
DOIs
Publication statusPublished - Mar 18 2020

    Fingerprint

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Guo, Q. H., Zhou, J., Mao, H., Qiu, Y., Nguyen, M. T., Feng, Y., Liang, J., Shen, D., Li, P., Liu, Z., Wasielewski, M. R., & Fraser Stoddart, J. (2020). TetrazineBox: A Structurally Transformative Toolbox. Journal of the American Chemical Society, 142(11), 5419-5428. https://doi.org/10.1021/jacs.0c01114