Chemical Science, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
An overview of structural responses helicenes with increasing dimensions and complexity to stepwise electron addition reveals charge- topology-dependent outcomes ranging from reversible irreversible core transformations site-specific reactivity.
Language: Английский
Chemical Communications, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
Dimerization of 20π antiaromatic indeno[2,1- c ]fluorene scaffolds by linking carbons 5 and 5′ is the key to producing an open-shell biindenofluorene isomer with small HOMO−LUMO singlet–triplet energy gaps.
Language: Английский
Citations
0
The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: March 19, 2025
Polycyclic aromatic hydrocarbons (PAHs) with open-shell or redox characteristics are highly desirable due to their intriguing electronic properties and potential applications. Here, we demonstrate a series of phenylenediamine-linked nanographenes (NGs) 1–3 by connecting two aza-hexa-peri-hexabenzocoronene (HBC) units p-phenylene, p,p'-biphenylene, p,p"-terphenylene, respectively, unveil 3D conformations, structures, properties. As proved X-ray crystallographic analysis quantum chemical calculation, adopted anti-folded, Z-shaped structures rotatable single bonds. The structure-dependent capabilities were disclosed. For 1, stable monoradical cation was generated one-electron oxidation as the terminal product. revealed an unprecedented syn-folded structure 1+. However, 2 3 demonstrated redox-active molecules from neutral dication that each oxidative state can be precisely controlled oxidation/reduction.
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: March 24, 2025
In this paper, we report redox-active azacoronene helicenes obtained through nucleophilic substitution of fluorinated with 3,4-diethylpyrrole, followed by Scholl reactions. Cyclic voltammetry these compounds displays reversible oxidation events at low potentials. The oxidized species display distinct optical properties. Additionally, incorporated the azacoronene/helicene unit into conjugated polymers.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: April 11, 2025
The modulation of molecular recognition underpins numerous wide-ranging applications and has inspired the development a myriad switchable receptors, in particular photo- or redox-responsive hosts. Herein, we report highly versatile three-state cation receptor family switch system based on an overcrowded alkene strapped with crown ethers, which can be switched by both redox light stimuli, thereby combining advantages approaches. Specifically, neutral switches quantitatively converted between anti- syn-folded geometries irradiation, leading to discovery significant increase decrease binding affinity, was exploited shuttle pseudorotaxane-forming dibenzylammonium guest ethers slightly different sizes. Alternatively, two-electron oxidation orthogonal, dicationic, nonvolatile state completely turns off host, ejecting guest. Upon reduction, metastable is first formed, then thermally relaxes, resulting unique, autonomous, cation-dependent multistate switching cascade.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31892 - 31900
Published: Nov. 5, 2024
The ubiquitous ability of natural dynamic nanostructures to adapt environmental changes is a highly desirable property for chemical systems, particularly in the development complex matter, molecular machines, and life-like materials. Designing such systems challenging due generation mixtures with responses that are difficult predict, characterize, diversify. Here, we navigate between self-assembled architectures using light by operating an intrinsic photoswitchable building block governs state system. When complementary units present, photoswitch determines predominant architecture, reversibly adapting cage macrocycles, including (otherwise inaccessible) higher-energy assemblies. Our study showcases this concept seven different transformations, offering unprecedented degree control, diversification, adaptation self-selecting units. These findings could enable applications on-demand dissipative macrocycles based on bonds. We also envision transient nanostructures, e.g., reticular polymeric materials, being explored fine-tuning nature unit.
Language: Английский
Citations
3
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 13, 2024
Overcrowded alkenes have received considerable attention as versatile structural motifs in a range of optical switches and light-driven unidirectional motors. In contrast, their actuation by electrochemical stimuli remains underexplored, even though this alternative energy input may be preferred various applications enables additional control over molecular switching states properties. While symmetric bistricyclic overcrowded enes (BAEs) containing two identical halves based on either thioxanthene (TX) or acridine (Acr) are known to reversible conformational redox switches, potentials generally too high low, respectively, thereby preventing wider applications. Herein, we demonstrate that the "mixed" TX-Acr switch possesses properties lie between those its parent analogs, enabling interconversion three stable at mild potentials. This includes neutral
Language: Английский
Citations
1
Chemical Science, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
An overview of structural responses helicenes with increasing dimensions and complexity to stepwise electron addition reveals charge- topology-dependent outcomes ranging from reversible irreversible core transformations site-specific reactivity.
Language: Английский
Citations
0