Facile Synthesis of Donor–Acceptor Heterocycloarenes Based on Pyrazine Derivatives Possessing Intriguing Iodide Ion Capture Properties

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21922 - 21931

Published: July 25, 2024

Donor–acceptor (D–A) conjugated systems have been extensively investigated and play important roles in organic electronics. Incorporating D–A structures into (hetero)cycloarenes endows them tunable electronic properties, while the well-defined cavity remains. However, synthetic complexity of introducing electron-acceptor moieties limits their development applications. In this paper, first family electronically heterocycloarenes (DAHCn, n = 1–5) based on pyrazine derivatives was facilely synthesized through cyclocondensation reaction from a tetraketone-functionalized heterocycloarene precursor prepared using ketal-protection strategy. The effect expanded conjugation inserted electron-withdrawing group studied systematically by X-ray crystallographic analysis, various spectroscopic measurements, theoretical calculations. Interestingly, presence an polarizes inner C(sp2)–H significantly increases binding affinities to iodide anion. Meanwhile, anion affinity can be further modulated type attached substituents distance polarization. More importantly, dicyanopyrazine derivative DAHC3 shows highest strength ion as 2:1 sandwich complex (log β2 12.3 ΔG −69.1 kJ mol–1), which is strongest receptor hydrogen bonding interactions reported date. Our finding provides new strategy design synthesize strong receptors.

Language: Английский

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Manipulating Crystal Packing and Self-Assembly by π-Extended and Isomeric Fused Strategies in Thiophene Ring-Terminated Polycyclic Aromatic Hydrocarbons

Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 1048 - 1053

Published: Jan. 21, 2025

Two series of polycyclic aromatic hydrocarbon isomers (PT-2 and PT-3, P2T-V P2T-C) were designed synthesized by isomerically fusing phenanthrene with thiophene thieno[3,2-b]thiophene, respectively. All the new target molecules confirmed single-crystal X-ray analysis, it was found that solid-state packing can be effectively modulated through a combination π-extended isomeric fused strategies. Meanwhile, compared ring-terminated PT-2 both having V-shaped geometry showing no obvious self-assembly behavior, unit thieno[3,2-b]thiophene-terminated isomer displays structure moderate properties P2T-C exhibits C-shaped configuration further enhanced properties.

Language: Английский

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Design Strategies, Properties, and Applications toward Cycloarenes and Heterocycloarenes

Accounts of Materials Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Language: Английский

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Tuning Molecular Packing and Boosting Self-Assembling Properties via Ring Fusion Strategy in Naphthalimide-Based A–D–A Conjugated Systems

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 5010 - 5015

Published: May 31, 2024

Two fully fused acceptor–donor–acceptor (A–D–A) architecture conjugated derivatives (NPF and NCF) comprising an electron-withdrawing naphthalimide (NMI) two different electron-donating cores, phenanthrene carbazole, respectively, were conveniently synthesized by bismuth(III)-catalyzed selective cyclization of vinyl ethers. Compared with their corresponding single bond-linked A–D–A molecules NPS NCS, both having a moderately twisted aromatic configuration, the ring fusion strategy leads to coplanar skeletons greatly changes electronic structures, photophysical properties, self-assembling behaviors, molecular packing motifs. In particular, naphthalimide/carbazole derivative NCF exhibits intriguing 2D brickwork significantly enhanced properties.

Language: Английский

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