Synthesis and optical properties of mono- and diaminocorannulenes

Xie, Feng; Finney, Nathaniel S.

doi:10.1039/d0cc03853a

“…Compared with pristine corannulene, the quinolizinium-fused corannulenes 11a – 12b exhibit enhanced solubility in various organic solvents. The incorporation of cationic nitrogen atoms enhances both solubility and fluorescence properties, endowing these curved PAH salts with potential for biological and supramolecular applications …”

Section: Resultsmentioning

confidence: 99%

“…The incorporation of cationic nitrogen atoms enhances both solubility and fluorescence properties, endowing these curved PAH salts with potential for biological and supramolecular applications. 83 …”

Section: Resultsmentioning

confidence: 99%

Extended Quinolizinium-Fused Corannulene Derivatives: Synthesis and Properties

Huang,

Wang,

Fu

et al. 2024

JACS Au

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Reported here is the design and synthesis of a novel class of extended quinolizinium-fused corannulene derivatives with curved geometry. These intriguing molecules were synthesized through a rationally designed synthetic strategy, utilizing double Skraup–Doebner–Von Miller quinoline synthesis and a rhodium-catalyzed C–H activation/annulation (CHAA) as the key steps. Single-crystal X-ray analysis revealed a bowl depth of 1.28–1.50 Å and a unique “windmill-like” shape packing of 12a(2PF 6 – ) due to the curvature and incorporation of two aminium ions. All of the newly reported curved salts exhibit green to orange fluorescence with enhanced quantum yields (Φf = 9–13%) and improved dispersibility compared to the pristine corannulene (Φf = 1%). The reduced optical energy gap and lower energy frontier orbital found by doping extended corannulene systems with nitrogen cations was investigated by UV–vis, fluorescence, and theoretical calculations. Electrochemical measurements reveal a greater electron-accepting behavior compared with that of their pyridine analogues. The successful synthesis, isolation, and evaluation of these curved salts provide a fresh perspective and opportunity for the design of cationic nitrogen-doped curved aromatic hydrocarbon-based materials.

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Five‐Fold Symmetric Pentaindolo‐ and Pentakis(benzoindolo)Corannulenes: Unique Structural Dynamics Derived from the Combination of Helical and Bowl Inversions

Kise

¹

,

Ooi

²

,

Saito

³

et al. 2021

Angewandte Chemie

7

0

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Peripherally p-extended corannulenes bearing quintuple azahelicene units, 10 and 11,w ere prepared and their dynamic behaviors were studied experimentally and theoretically.T he fused corannulenes were synthesized from sympentabromocorannulene in three steps.X -Rayd iffraction analysis for 10 displayed aconformer possessing aP(M) bowl chirality and aP PMPM (PMPMM) helical chirality,w hich was found to be the most stable conformer(s). Variabletemperature NMR measurements of 10 and 11 revealed that their structural isomers can be interconvertible in solution, depending on the steric congestion around the helical scaffolds. Automated search for conformers in the equilibrium and transition states by Artificial Force Induced Reaction (AFIR) method revealed their interconversion networks,i ncluding bowl-inversion and helical-inversion. This analysis indicated that the co-existing corannulene and azahelicene moieties influence the conformational dynamics,w hich leads to mitigation of the activation energy barriers for isomerization.

show abstract

Five‐Fold Symmetric Pentaindolo‐ and Pentakis(benzoindolo)Corannulenes: Unique Structural Dynamics Derived from the Combination of Helical and Bowl Inversions

Kise

¹

,

Ooi

²

,

Saito

³

et al. 2021

View full text Add to dashboard Cite

Peripherally p-extended corannulenes bearing quintuple azahelicene units, 10 and 11,w ere prepared and their dynamic behaviors were studied experimentally and theoretically.T he fused corannulenes were synthesized from sympentabromocorannulene in three steps.X -Rayd iffraction analysis for 10 displayed aconformer possessing aP(M) bowl chirality and aP PMPM (PMPMM) helical chirality,w hich was found to be the most stable conformer(s). Variabletemperature NMR measurements of 10 and 11 revealed that their structural isomers can be interconvertible in solution, depending on the steric congestion around the helical scaffolds. Automated search for conformers in the equilibrium and transition states by Artificial Force Induced Reaction (AFIR) method revealed their interconversion networks,i ncluding bowl-inversion and helical-inversion. This analysis indicated that the co-existing corannulene and azahelicene moieties influence the conformational dynamics,w hich leads to mitigation of the activation energy barriers for isomerization.

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Synthesis and optical properties of mono- and diaminocorannulenes

Abstract: The synthesis and luminescence properties of a series of mono- and diaminocorannulenes are described herein. Their synthesis from halocorannulenes is straightforward. Evaluation of their luminescence leads to three surprising discoveries....

Cited by 5 publications

References 44 publications

Extended Quinolizinium-Fused Corannulene Derivatives: Synthesis and Properties

Extended Quinolizinium-Fused Corannulene Derivatives: Synthesis and Properties

Five‐Fold Symmetric Pentaindolo‐ and Pentakis(benzoindolo)Corannulenes: Unique Structural Dynamics Derived from the Combination of Helical and Bowl Inversions

Five‐Fold Symmetric Pentaindolo‐ and Pentakis(benzoindolo)Corannulenes: Unique Structural Dynamics Derived from the Combination of Helical and Bowl Inversions

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