Computed nucleus-independent chemical shifts (NICS), contour plots of isotropic magnetic shielding (IMS), and gauge-including magnetically induced current (GIMIC) plots suggest that polarization of the π-system of acridones may perturb the numbers and positions of Clar sextet rings. Decreasing numbers of Clar sextets are connected to experimental observations of a narrowing HOMO-LUMO gap and increased charge mobility in solid-state assemblies of quinacridone and epindolidione.
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http://dx.doi.org/10.1039/d1ob01720a | DOI Listing |
J Phys Chem Lett
January 2025
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bengaluru 560012, India.
The synthesis of organic radicals continues to garner significant interest due to their fascinating optical, electronic, and magnetic properties. Moreover, the growing demand for chemically stable organic radicals is driven by the rapid expansion of the market for electronic devices utilizing organic semiconductors. In this context, the development of multifaceted approaches for the design of stable organic radicals is of great importance.
View Article and Find Full Text PDFBeilstein J Org Chem
December 2024
School of Pharmaceutical Science and Technology, Tianjin University, Tianjin, PR China.
Quantitative assessment of the first acidity constant (p ) for BFC (27.6 in CHCN) and FIC (27.8 in CHCN) shows the methylene protons to be significantly more acidic than those in related cyclopentadiene (32 in CHCN), indene (34 in CHCN), or fluorene (37 in CHCN) and comparable to the methine of 9-perfluorophenylfluorene (28.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Chemical Engineering, Inha University, Incheon 22212, Republic of Korea.
Two contradictory theories, Clar's sextet and resonance theory, explain the stability of conjugated macrocycles using localized and delocalized models, respectively. To reconcile these theories and gain better insights, PAH-containing porphyrinoids were chosen as a representative class of conjugated macrocycles. Two types of Clar's sextets were identified and proposed for the first time based on their interaction with global conjugated pathways: (i) shared sextets that integrate with and perturb the global resonance pathway, and (ii) independent sextets that are separate from the pathway and potentially stabilize or do not perturb it.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, Indian Institute of Technology Ropar Rupnagar 140001 Punjab India
Nakano reported that the antiaromatic indenofluorene (IF) isomers are diradicaloid molecules having varying degrees of open-shell character, with indeno[1,2-]fluorene displaying a weaker diradical character index ( = 0.072). Unlike 6,12-trimethylsilylethynyl disubstituted [1,2-]IF, the 6,12-aryl disubstituted [1,2-]IF derivatives did not show any experimental evidence of diradical properties.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Center of Single-Molecule Sciences, Institute of Modern Optics, Tianjin Key Laboratory of Micro-Scale Optical Information Science and Technology, College of Electronic Information and Optical Engineering, Nankai University, 38 Tongyan Road, Jinnan District, 300350, Tianjin, China.
High-spin organic radicals are notable for their unique optical, electronic, and magnetic properties, but synthesizing stable high-spin systems is challenging due to their inherent reactivity. This study presents a novel strategy for designing stable high-spin polycyclic hydrocarbons (PHs) by incorporating allylic radical into fused aromatic benzenoid rings. To enhance stability, large steric hindrance groups with a synergistic captodative effect were added to the allylic radical centers.
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