Regulating Steric Effect of Cobalt Corroles for Promoted Oxygen Electrocatalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14350 - 14355

Published: Sept. 13, 2024

Language: Английский

---

Topology-Directed Synthesis of Helical Phosphoniums with High Diradical Character and Polar-Dependent Electron Transfer

Chemistry of Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 14, 2024

Molecular topology synthesis of polycyclic aromatic hydrocarbons (PAHs) with diradical character takes root in intramolecular coupling breakthrough. Herein, we report selective Mn(III)/Cu(II)-mediated C–P and C–H bond cleavage to obtain robust donor-fused phosphoniums helical or planar geometries distinct cationic charges. The former structures incorporate a common phospha[5]helication acceptor different arylamine donors, the latter structure contains phospha[6]dication same donors. These unprecedented ionic salts hold distinguishing donor–acceptor (D–A) constructions, showing unique topology-dependent optoelectronic properties. folded radical ammoniums possess an extreme electron-deficient state through-space isolation high (y0 = 0.989). Moreover, tunable charge transfer (CT) locally excited (LE) transition components facilitate diverse hybridized local (HLCT) solvents, endowing highest emission band gap variation 0.78 eV (∼217 nm). fluorescence radiation could also be adjusted from blue near-infrared regions via tailoring polar-dependent states, which output additional circularly polarized luminescence compatible chiral menthol matrix elevated quantum efficiency undisturbed deep-red glow. It is worth mentioning that atomically precise Mn(III) halide has been unprecedentedly captured determined for activation.

Language: Английский

---

Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 5, 2024

Abstract We describe effective development of the highly diastereoselective synthesis double helical tetraamine 2-H2-C2 and propose a mechanism for its formation. The resolution is facilitated by high racemization barrier 43 kcal mol–1 it implemented via either chiral auxiliary or preparative supercritical fluid chromatography. This enables preparation first high-spin neutral diradical, with spin density delocalized within an enantiomeric π-system. presence two 3-electron C–N bonds in diradical leads to: (1) triplet (S = 1) ground state singlet-triplet energy gap 0.4 (2) long half-life up to 6 days 2-MeTHF at room temperature. possesses least 26 293 K chiroptical properties, absorption anisotropy factor |g| ≈ 0.005 548 nm. These unique magnetic optical properties our form basis next-generation spintronic devices. 1 Introduction 2 Synthesis Resolution C 2-Symmetric Double Helical Tetraamine 2-H2-C 3 Characterization Neutral High-Spin Aminyl Diradical 22• -C 4 Conclusion

Language: Английский

---

Anion-dependent ion-pairing assemblies of triazatriangulenium cation that interferes with stacking structures

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2567 - 2576

Published: Oct. 10, 2024

Ion pairs of N -(2,6-dimethylphenyl)-substituted triazatriangulenium (TATA + ) cation with various counteranions were synthesized to investigate the interactions for bulky cation. Single-crystal X-ray analysis TATA ion revealed solid-state ion-pairing assemblies without stacking at cationic π-planes. The showed counteranion-dependent assembly structures, smaller located top and bulkier displaced from plane interact surrounding .

Language: Английский

---