On the Cation-π capabilities of infinitene (∞). Evaluation of bonding and circular dichroism properties for Infinitene-Ag(I)n (n = 1–4) complexes from relativistic DFT calculations

Ulloa, Carolina Olea; Guajardo‐Maturana, Raul; Muñoz-Castro, Álvaro

doi:10.1016/j.poly.2023.116323

Cited by 5 publications

(6 citation statements)

References 79 publications

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“…Given that inherent chirality is still scarcely known in carbon nanostructures, the potential exploitation of infinitenes as chiroptic materials holds promise and challenges. As another relevant application, generalized infinitenes with macrocyclic cavities of different sizes and shapes could be used as cavitands in host–guest chemistry for molecular recognition and sensing, bioimaging, drug delivery, nonlinear optics, etc. , In particular, the combination of chirality and host–guest chemistry might result in interesting applications in chiroptics and chiral catalyst screening …”

Section: Discussionmentioning

confidence: 99%

“…In particular, the rigid structural configuration endows each enantiomer with persistent topological chirality and, consequently, interesting circularly polarized luminescence (CPL) characteristics . Several further quantum chemistry calculations were carried out in a timely manner to uncover the aromaticity, − chiroptical and optoelectronic properties, , excited-state dynamics, and π-complexation with Ag cations of this new compound. These nascent investigations all suggest that infinitene, as a new form of nanocarbons, is of both fundamental and practical importance with potential applications in chiroptics, optoelectronics, asymmetric synthesis, supramolecular chemistry, and perhaps other fields.…”

Section: Introductionmentioning

confidence: 99%

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Infinitenes as the Most Stable Form of Cycloarenes: The Interplay among π Delocalization, Strain, and π–π Stacking

Wang

2023

J. Am. Chem. Soc.

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The recent successful preparation of infinitene has sparked widespread attention due to its aesthetic appeal and synthetic challenge. Spectroscopic measurements and follow-up computational investigations suggest that infinitene holds fundamental significance and potential applications in chiroptics, optoelectronics, asymmetric synthesis, and supramolecular chemistry. However, unlike other looped polyarenes enriched with sizes and shapes, the infinitene molecule seems, so far, the only known example of this fascinating new form of nanocarbons, whose further exploitation would be considerably limited because of the lack of molecular diversity. Here, we introduce a whole new family of generalized infinitenes with different sizes and topologies. Three types of infinitene structures are rationally designed by joining two units of coronene, kekulene, or their extended analogs. The constructed molecules of varying sizes, each with a large number of possible topoisomers, are systematically studied by DFT calculations. Comprehensive analysis using a simple energy decomposition model uncovers that the stability of infinitenes is governed by the interplay among π delocalization, steric strain, and π–π stacking. While the first two factors are crucial to the stability of smaller infinitenes, the latter is the primary stabilizing interaction for larger infinitenes. Most importantly, we show that larger-sized infinitenes are actually the energetically most favorable form among all known looped polyarenes; their substantial thermodynamic stability surpassing that of circulenes, various carbon nanobelts, and kekulene-like macrocycles renders them promising targets for synthesis. The simulated 1H NMR, UV–vis, and circular dichroism spectra along with optical rotations for the most stable infinitene species may help their identification in future synthetic efforts.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Infinitenes as the Most Stable Form of Cycloarenes: The Interplay among π Delocalization, Strain, and π–π Stacking

Wang

2023

J. Am. Chem. Soc.

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“…Cycloarenes are a class of fully fused macrocyclic aromatic hydrocarbons comprising angular and linear annellations of benzene units enclosing a cavity into which C-H bonds point. 1 Due to their remarkable properties and potential applications in optoelectronics, 2,3 synthetic chemistry, [4][5][6] supramolecular chemistry, 7,8 etc., cycloarenes have attracted the scientific community for decades. 5 In addition, the large cavity structure offers cycloarenes some promising applications in host-guest chemistry.…”

Section: Introductionmentioning

confidence: 99%

Generalized kekulenes and clarenes as novel families of cycloarenes: structures, stability, and spectroscopic properties

Du,

Wang

2024

Phys. Chem. Chem. Phys.

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“…X-ray crystal structure analysis has shown that the combined lamellar and herringbone-like packing structure introduced three-dimensional electronic interactions caused by the infinity shape. Since this report, fascinating properties of infinitene have been predicted. − Wu and Isobe et al synthesized a twisted CNB in 2021 and a fused [5]helicene dimer in 2023 , as a related molecule of infinitene. In addition to aromatic hydrocarbon-based CNBs, heteroatom-embedded CNBs have also been reported. − In 2019, Tanaka et al synthesized the first oxygen-embedded CNB by rhodium-catalyzed alkyne cyclotrimerization .…”

Section: Synthesis Of Cnbs and Related Aromatic Beltsmentioning

confidence: 99%

Carbon Nanobelts: Brief History and Perspective

Imoto,

Yagi,

Itami

2023

Precision Chemistry

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Carbon nanotubes (CNTs) are an emerging nanomaterial because of their outstanding performance in various applications. In recent years, the segment molecules of CNTs, referred to as carbon nanorings (CNRs) or carbon nanobelts (CNBs), have gained attention for their unique structures and properties, as well as their potential as seed molecules for the precise synthesis of CNTs. CNBs are rigid and thick segments of CNTs whose synthesis has been addressed by scientists fascinated by the uniqueness of CNBs long before the discovery of CNTs. After 60 years of efforts by synthetic chemists all over the world, the synthesis of the first CNB, (6,6)CNB, was achieved by our group in 2017. Since this milestone, diverse types of nanobelts have been synthesized through various synthetic routes, thereby demonstrating their photophysical, magnetic, and redox properties derived from rigid belt structures. The applications of CNBs have also been introduced recently. The formation of the host–guest complex, transformation to three-dimensional molecules, and measurement of conductivity have been reported for CNBs. This paper summarizes the brief history and perspective of CNBs. Further synthetic campaigns and aggressive application of CNBs would create novel and groundbreaking scenes in materials science.

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On the Cation-π capabilities of infinitene (∞). Evaluation of bonding and circular dichroism properties for Infinitene-Ag(I)n (n = 1–4) complexes from relativistic DFT calculations

Cited by 5 publications

References 79 publications

Infinitenes as the Most Stable Form of Cycloarenes: The Interplay among π Delocalization, Strain, and π–π Stacking

Infinitenes as the Most Stable Form of Cycloarenes: The Interplay among π Delocalization, Strain, and π–π Stacking

Generalized kekulenes and clarenes as novel families of cycloarenes: structures, stability, and spectroscopic properties

Carbon Nanobelts: Brief History and Perspective

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