A Review of Crystalline Multibridged Cyclophane Cages: Synthesis, Their Conformational Behavior, and Properties

Zhang, Xingxing; Li, Jian; Niu, Yun‐Yin

doi:10.3390/molecules27207083

Cited by 8 publications

(4 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Multibridged cyclophanes have attracted attention as supramolecular building blocks, such as electron donors [ 38 ] and cage compounds for noble gas atoms [ 39 ]. Various cyclophane derivatives with different ring distances have been reported.…”

Section: Discussionmentioning

confidence: 99%

Molecular-Simulation–Inspired Synthesis of [6]-Prismane via Photoisomerisation of Octafluoro[2.2]paracyclophane

Hosokawa,

Kajiya,

Ohshima

et al. 2024

Molecules

View full text Add to dashboard Cite

Prismanes have been attracting interest for nearly 50 years because of their geometric symmetry, highly strained structures, and unique applications due to their high carbon densities and bulky structures. Although [3]-, [4]-, and [5]-prismanes have been synthesised, [6]-prismanes and their derivatives remain elusive. Herein, fluorine chemistry, molecular mechanics, molecular orbital package, and density functional theory calculations were used to design and implement the photoisomerisation of octafluoro[2.2]paracyclophane (selected based on the good overlap of its lowest unoccupied molecular orbitals and short distance between the benzene rings) into octafluoro-[6]-prismane. Specifically, a dilute solution of the above precursor in CH3CN/H2O/dimethyl sulfoxide (DMSO) (2:1:8, v/v/v) solution was irradiated with ultraviolet light, with the formation of the desired product confirmed through the use of nuclear magnetic resonance spectroscopy and gas chromatography–mass spectrometry. The product was thermally stable in solution but not under work-up conditions, which complicated the further analysis and single-crystal preparation. The key criteria for successful photoisomerisation were the presence of fluorine substituents in the cyclophane structure and DMSO in the solvent system. A more stable derivative design requires the isolation of prismane products. The proposed fluorination-based synthetic strategy is applicable to developing novel high-strain molecules/materials with three-dimensional skeletons.

show abstract

Section: Discussionmentioning

confidence: 99%

Molecular-Simulation–Inspired Synthesis of [6]-Prismane via Photoisomerisation of Octafluoro[2.2]paracyclophane

Hosokawa,

Kajiya,

Ohshima

et al. 2024

Molecules

View full text Add to dashboard Cite

show abstract

“…Organocatalysis is widely accepted as a popular field of catalysis where the organic compounds based on carbon, hydrogen, nitrogen, oxygen, sulfur, and phosphorus are used as catalysts for organic transformations. , Many organocatalysts have been designed to perform organic synthesis, including the asymmetric synthesis. , Cyclophane is an important class of supramolecular compounds containing a bridged aromatic ring. In general, any aromatic ring bridged by at least one aliphatic n-membered bridge with n ≥ 0 is termed a cyclophane. − Cyclophanes with a heterocyclic ring system possess a favorable binding site for host–guest chemistry, catalysis, − and self-assembly. , Imidazolium and benzimidazolium-containing cyclophanes have been applied in host–guest chemistry. − 3D cyclophanes containing benzimidazolium moiety have been reported before as anion receptors , and carrier vehicles for anticancer drug delivery . Herein, we report a novel cyclophane based on a benzimidazolium moiety.…”

Section: Introductionmentioning

confidence: 96%

3D Cyclophane for the Selective Conversion of Epoxide to Cyclic Carbonate

Roy,

Kar,

Paul

et al. 2023

J. Org. Chem.

View full text Add to dashboard Cite

A novel three-dimensional (3D) cyclophane molecule 1 was synthesized and fully characterized. Cyclophane 1, which can form a N heterocyclic carbene, was tested for conversion of certain epoxides (3−6) [scheme 2] to cyclic carbonates in the presence of CO 2 . Propylene oxide (3) was found to have more reactivity with cyclophane 1 compared to the other epoxides. The theoretical calculations based on N,N′-disubstituted imidazol(in)ium-2-carboxylates derived from N,N′ disubstituted imidazole as the source of N-heterocyclic carbene show lower activation energy in the case of the reactivity of epoxides 5 and 6 as compared to 3 and 4. However, cyclophane 1, which possesses a 3D geometry, can form the open intermediate with CO 2 and propylene oxide more feasibly than the other three epoxides, which have larger sizes as compared to propylene oxide. Hence, the reaction of propylene oxide, CO 2 , and cyclophane 1 can follow the mechanistic path 1, whereas the epoxides 4−6 can follow a different mechanistic path 2. Cyclophane 1 is the first example of a cyclophane to act as an organocatalyst for the conversion of CO 2 and epoxide to cyclic carbonate via the N heterocyclic carbene pathway.

show abstract

“…Undoubtedly, superphanes constitute the most unusual subgroup of cyclophanes [1][2][3]. This uniqueness is primarily related to the aesthetically beautiful symmetry of their structure, most often comparable with a six-bladed pinwheel, a lantern, or a barrel.…”

Section: Introductionmentioning

confidence: 99%

Characteristics of Intermolecular Interactions between Encapsulated Molecules and the Lantern-Like Carcerand Superphanes

Jabłoński

2024

Molecules

View full text Add to dashboard Cite

The main topic of the article is to provide the characteristics of individual intermolecular interactions present between three lantern-like superphanes and the H2O, NH3, HF, HCN, and MeOH molecules trapped inside them. Despite the large cavity, the freedom of the trapped molecules is significantly limited by the presence of numerous interaction sites on the side chains of the superphane molecule. It is shown that the molecule trapped inside the superphane is stabilized mainly by only one or, less often, two strong hydrogen bonds involving the imino nitrogen atom, but QTAIM calculations also suggest the presence of many other intermolecular interactions, mainly hydrogen bonds involving imino or central hydrogen atoms from the side chains of the superphane molecule. Moreover, it is also shown that the structural simplification of the side chains does not significantly affect both the size of the superphane molecule and the obtained encapsulation energies, which is important in modeling this type of carceplexes. Noticeably, the parent superphane considered here was previously synthesized by the group of Qing He, so the results obtained will help in understanding this type and similar systems.

show abstract

A Review of Crystalline Multibridged Cyclophane Cages: Synthesis, Their Conformational Behavior, and Properties

Cited by 8 publications

References 69 publications

Molecular-Simulation–Inspired Synthesis of [6]-Prismane via Photoisomerisation of Octafluoro[2.2]paracyclophane

Molecular-Simulation–Inspired Synthesis of [6]-Prismane via Photoisomerisation of Octafluoro[2.2]paracyclophane

3D Cyclophane for the Selective Conversion of Epoxide to Cyclic Carbonate

Characteristics of Intermolecular Interactions between Encapsulated Molecules and the Lantern-Like Carcerand Superphanes

Contact Info

Product

Resources

About