A surface adlayer is generated on organic single crystals (tetracene and rubrene) using the site specific Diels-Alder reaction and a series of vapor phase dienophiles. X-ray photoelectron spectroscopy (XPS) confirms adsorption on the surfaces of tetracene and rubrene and mass spectrometry demonstrates the reaction's applicability to a range of dienophiles.
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http://dx.doi.org/10.1039/c3cc40866c | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts, 02155, United States.
This paper describes a series of 12 9,10-dimethoxyanthracene derivatives functionalized with a range of electronically diverse ethynyl substituents at the 2 and 6 positions, aimed at tuning their optoelectronic properties and reactivity with singlet oxygen (O). Optical spectroscopy, cyclic voltammetry, and density functional theory calculations reveal that the ethynyl groups decrease the HOMO-LUMO gaps in these acenes. Notably, bis(dimethylanilineethynyl) substituents increase the wavelength of absorbance onset by over 60 nm compared to 9,10-dimethoxyanthracene (DMA).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
IITH: Indian Institute of Technology Hyderabad, Chemistry, Kandi, Sangaredddy, 502285, INDIA.
A squaramide-based monomer, designed for topochemical azide-alkyne cycloaddition (TAAC) polymerization, crystallizes as two polymorphs, M1 and M2, both having crystal packing suitable for topochemical polymerization. The hydrogen-bonding between squaramide units bias the molecular organization in both the polymorphs. 3D packing of H-bonded stacks of monomer lead to juxtaposition of azide and alkyne units of adjacent molecules in a transition-state-like arrangement for their regiospecific cycloaddition reaction.
View Article and Find Full Text PDFOrg Lett
January 2025
Institute of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan.
Multiple Diels-Alder reactions are a powerful method to construct large asymmetric scaffolds, but these reactions often produce numerous isomers. We now report a triple Diels-Alder reaction between a cyclic furan trimer and -substituted maleimides, achieving selective synthesis of a single asymmetric tris-adduct. The stereoselectivity of cycloaddition to π-extended furan derivatives was clarified by the experimental analysis of intermediates and theoretical calculations.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, c/Maria Aurèlia Capmany 69, 17003 Girona, Catalonia, Spain.
Both silicon and carbon are elements located in group 14 on the periodic table. Despite some similarities between these two elements, differences in reactivity are important, and whereas carbon is a central element in all known forms of life, silicon is barely found in biological systems. Here, we investigate the Diels-Alder cycloaddition reaction of cyclopentadiene (CP) and cyclopentasildiene (CP) with fullerenes C, Li@C, Si, and Li@Si using density functional theory methods.
View Article and Find Full Text PDFChem Soc Rev
January 2025
Pingyuan Laboratory, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007, Henan, P. R. China.
The use of olefins in the construction of cyclic compounds represents a powerful strategy for advancing the pharmaceutical industry. Photocycloaddition has attracted significant interest from chemists due to its ability to exploit simple and readily available olefins along with their reaction patterns under mild conditions. Moreover, the sustainable and versatile pathways for generating highly reactive intermediates can greatly enrich both substrate diversity and reaction patterns.
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