Modulating Supramolecular Charge-Transfer Interactions in the Solid State using Compressible Macrocyclic Hosts

Jia-Rui Wu; Dongxia Li; Gengxin Wu; Meng-Hao Li; Ying-Wei Yang

doi:10.1002/anie.202210579

Modulating Supramolecular Charge-Transfer Interactions in the Solid State using Compressible Macrocyclic Hosts

Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202210579. doi: 10.1002/anie.202210579. Epub 2022 Sep 27.

Authors

Jia-Rui Wu^{1

2}, Dongxia Li¹, Gengxin Wu¹, Meng-Hao Li¹, Ying-Wei Yang¹

Affiliations

¹ International Joint Research Laboratory of Nano-Micro Architecture Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, P. R. China.
² Key Laboratory of Automobile Materials of Ministry of Education and School of Materials Science and Engineering, Jilin University, 5988 Renmin Street, Changchun, 130025, P. R. China.

PMID: 36073559
DOI: 10.1002/anie.202210579

Abstract

Modulating intermolecular charge-transfer (ICT) interactions between specific donor and acceptor species in host-guest systems is a big challenge and full of research value in supramolecular chemistry and materials science. In this work, a strategy to modulate the supramolecular ICT interactions in the solid state is developed by compressing the binding cavity of a macrocyclic host named perethylated leaning pillar[6]arene (p-EtLP6). The solid-state ICT affinities of p-EtLP6 toward multi-types of electron-deficient planar guests could be significantly enhanced by transforming the macrocyclic backbone from the original para-bridged mode into a hybrid para- and meta-bridged isomeric form (m-EtLP6). X-ray single-crystal structural analyses incorporating theoretical calculation demonstrate that the improved ICT affinities are mainly attributed to the superior host-guest size fit arising from the compressed binding cavity in m-EtLP6 as compared with p-EtLP6.

Keywords: Co-Crystals; Host-Guest Chemistry; Intermolecular Charge-Transfer; Macrocycles; Superstructures.

Abstract

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