Structurally diverse macrocycle co-crystals for solid-state luminescence modulation

Bin Li, Lingling Liu, Yuan Wang, Kun Liu, Zhe Zheng, Shougang Sun, Yongxu Hu, Liqiang Li and Chunju Li ()
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Bin Li: Tianjin Normal University
Lingling Liu: Tianjin Normal University
Yuan Wang: Tianjin Normal University
Kun Liu: Tianjin Normal University
Zhe Zheng: Tianjin Normal University
Shougang Sun: Tianjin University
Yongxu Hu: Tianjin University
Liqiang Li: Tianjin University
Chunju Li: Tianjin Normal University

Nature Communications, 2024, vol. 15, issue 1, 1-8

Abstract: Abstract Organic co-crystals offer an opportunity to fabricate organic functional materials. Traditional co-crystals are generally packed following the segregated or mixed stacking mode, leading to the lack of structural and functional diversity. Herein, we report three sets of macrocycle co-crystals with identical co-constitutions. The macrocycle co-crystals differ in the stoichiometric ratios (2:1, 1:1, and 2:3) of the constituents and molecular packing modes. The co-crystals are constructed using triangular pyrene-macrocycle and 1,2,4,5-tetracyanobenzene exploiting exo-wall charge-transfer interactions. Interestingly, the three co-crystals exhibit distinct, tunable emission properties. The corresponding emission peaks appear at 575, 602, and 635 nm, covering yellow via orange to red. The X-ray diffraction analyses and the density functional theory calculations reveal the superstructure-property relationships that is attributed to the formation of different ratios of charge-transfer transition states between the donor and acceptor motifs, resulting in red-shifted luminescence.

Date: 2024
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DOI: 10.1038/s41467-024-46788-6

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