Bismacrocycle: Structures and Applications

Abstract

In the past half-century, macrocycles with different structures and functions, have played a critical role in supramolecular chemistry. Two macrocyclic moieties can be linked to form bismacrocycle molecules. Compared with monomacrocycle, the unique structures of bismacrocycles led to their specific recognition and assembly properties, also a wide range of applications, including molecular recognition, supramolecular self-assembly, advanced optical material construction, etc. In this review, we focus on the structure of bismacrocycle and their applications. Our goal is to summarize and outline the possible future development directions of bismacrocycle research.

Keywords: advanced optical materials; applications; bismacrocycle; self-assembly; supramolecular chemistry.

Scheme 1

Examples of bismacrocycles and related classification.

Figure 1

The 1 forms 2 with lanthanide cations, and 1 after UV illumination can further generate 3 with lanthanide cations, and 2 transforms to 3 after UV illumination, and then changes to 2 after heating. Reprinted with permission from ref. [39], copyright 2017 American Chemical Society.

Figure 2

Supramolecular assembly 5 formed between 4 and 6 through host-guest interaction and 7. Reprinted with permission from ref. [40], copyright 2018 Royal Society of Chemistry.

Figure 3

Schematic diagrams of light-controlled interchangeable supramolecular assembly 10 or 11 constructed between trans- or cis-8 and 9. Reprinted with permission from ref. [41], copyright 2019 Royal Society of Chemistry.

Figure 4

Representation of the stimuli-responsive chirality transfer and FRET between chiral donor 14 and achiral acceptor 12 in 13. Reprinted with permission from ref. [42], copyright 2019 Royal Society of Chemistry.

Figure 5

(a) Preparation of 16 from 15; (b) the stronger ductility as well as adhesion of 17. Reprinted with permission from ref. [43], copyright 2019 American Chemical Society.

Figure 6

Schematic representation of self-cross-linking supramolecular polymer network formation with 18. Reprinted with permission from ref. [44], copyright 2020 American Chemical Society.

Figure 7

Chemical structure of 19, 20, 21, and 25 (a); schematic illustration of spherical nanoparticles (24, 27) formed with 23 and 26 assemblies (b), also the photocontrolled energy transfer process in binary assembly 24 (c) and ternary assembly 27 (d). Reprinted with permission from ref. [49], copyright 2017 Wiley-VCH.

Figure 8

Chemical structure of 28, 30, and schematic illustration of their assembly. Reprinted with permission from ref. [50], copyright 2017 Wiley-VCH.

Figure 9

Chemical structure of 32, 33, and schematic representation of intercalation and photocleavage of DNA using 34. Reprinted with permission from ref. [51], copyright 2018 American Chemical Society.

Figure 10

Schematic representation of the preparation from host-guest interactions between 36 and the bifluorescent-emitting VIE guest 35 to generate supramolecular aggregates 37. Reprinted with permission from ref. [53], copyright 2018 Wiley-VCH.

Figure 11

Schematic representation of the helix interconversion of C₆₀-appended polyacetylene (40) directed by molecular recognition of 38 and 39. Reprinted with permission from ref. [54], copyright 2020 Royal Society of Chemistry.

Figure 12

Schematic diagram of the light synthesis of 43 and 44 from (E,E)-42 with the light-regulated length of (E,E)-41 and its derivatives. Reprinted with permission from ref. [55], copyright 2023 Royal Society of Chemistry.

Figure 13

The structure of 45 and its solid-phase fluorescence properties. Reprinted with permission from ref. [56], copyright 2020 Wiley-VCH.

Figure 14

Schematic illustration of the controllable light-harvesting nanosystem based on photo-modulation of the energy transfer pathway. Reprinted with permission from ref. [57], copyright 2021 Elsevier.

Figure 15

Schematic representation of the controlled assembly and photocatalytic process between 50 and guest 51–53. Reprinted with permission from ref. [58], copyright 2023 Wiley-VCH.

Figure 16

Chemical structure of 55, 56, and schematic illustration of the supramolecular polymerization of 57 and 59 (inset: photo of the supramolecular gels 57 and 59 under 365 nm UV light). Reprinted with permission from ref. [59], copyright 2022 American Chemical Society.

Figure 17

Chemical structure of 60, 61, 63, and schematic representation of the polymerisation degree adjustment between 60 and 61 via the introduction of 63, a pH-responsive competitive guest. Reprinted with permission from ref. [60], copyright 2017 Wiley-VCH.

Figure 18

(a) Structure of Bisheteracalixarenes (65–69) and 70; (b) schematic representation of 67 self-assembling with 70 to form coherent particles via anion-π interactions. Reprinted with permission from ref. [61], copyright 2019 American Chemical Society.

Figure 19

The structure of 71 and its luminescent properties. Reprinted with permission from ref. [62], copyright 2023 Wiley-VCH.

Figure 20

Synthesis of 73, 76–79 and schematic diagram of the preparation of AIE fluorescent nanomaterial 74 and 75 (a), schematic diagram of the preparation of AIE fluorescent nanomaterial (b). Reprinted with permission from refs. [64,65], copyright 2019 American Chemical Society and 2021 Elsevier.

Figure 21

Structure of 80 and schematic representation of 80 as a fluorescent sensor to detect 81. Reprinted with permission from ref. [66], copyright 2022 Elsevier.

Figure 22

(a) Structure of 82; (b) colocalization images of 82 with LysoTracker Red in RAW 264.7 cells; (c) photothermal images of 82 (0.1 mM) in the presence of E. coli under irradiation at 1 W cm⁻² for different times. (b,c) Reprinted with permission from ref. [67], copyright 2022 Wiley-VCH.

Figure 23

Confocal fluorescence imaging of the photothermal ablation induced by 88₂ ⊂ 83 upon irradiation at 1064 nm (top left); UV/Vis-NIR spectra of 84₂ ⊂ 83, 85₂ ⊂ 83, 86₂ ⊂ 83, and 88₂ ⊂ 83. Reprinted with permission from ref. [68], copyright 2023 Wiley-VCH.

Figure 24

Schematic synthesis of three TPE-containing pyridinium bismacrocycles 89–91. Reprinted with permission from ref. [69], copyright 2023 Elsevier.

Figure 25

(a) Construction of anionic regulated multi-component self-assembly structures based on biscalix[4]pyrrole 92; (b) The structure of 93 and its assembly with double N-oxides; (c) The structure of 94 and its assembly structure with two SO₄²⁻; (d) 95 specific recognition of F⁻; (e) 96 forms a 1:2 complex with F⁻ through different pathways. (a–e) Reprinted with permission from ref. [71,72,73,74,75], copyright 2017 Royal Society of Chemistry and 2017, 2020, 2022 American Chemical Society.

Figure 26

Synthesis of 97–98 and related fluorescence properties. Reprinted with permission from ref. [76], copyright 2020 Royal Society of Chemistry.

Figure 27

The structure of the 99 and a schematic diagram of its π-electronic system. Reprinted with permission from ref. [77], copyright 2019 American Chemical Society.

Figure 28

The synthetic strategy of 100–102 and its structure conversion. Reprinted with permission from ref. [78], copyright 2021 Wiley-VCH.

Figure 29

Synthesis of 103 and its single crystal structure. Reprinted with permission from ref. [79], copyright 2019 Wiley-VCH.

Figure 30

(a) The structure of 104–107; (b) The analogue structure of 104; (c) QCM airborne analyte sensing study of the title compounds as affinity materials relative to a passivated surface (denoted as “no affinity material”); (d) X-ray crystal structures of [9]CPP and 105. (b–d) Reprinted with permission from ref. [81], copyright 2020 American Chemical Society.

Figure 31

(a) The structure of 108 and the peanut-like complexation between 108 and 109 in a 1:2 ratio; (b) (b₁) Structure and properties of 110; (b₂) Fluorescence spectra of 110 in the solvent with different THF/H₂O ratios; (b₃) CIE 1931 chromaticity diagram of 110 in THF/H₂O mixtures; (b₄) r Emission colour changes of 110 from cyan to red in aqueous THF with f_w = 0–99 vol% under 365 nm UV light. Reprinted with permission from ref. [82,83], copyright 2021 Wiley-VCH and 2022 Nature Publishing Group.

Figure 32

(a) The structure of 111 and 112 (b) Solid-state structures of a complex of 112 and C₆₀ in a 1:1 ratio. Reprinted with permission from ref. [85], copyright 2021 American Chemical Society.

Figure 33

Crystal structure of a complex of 113 formed in a 1:2 ratio with C₆₀ or C₇₀. Reprinted with permission from ref. [86], copyright 2022 Wiley-VCH.