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Engineering perfluoroarenes for enhanced molecular barrier effect and chirality transfer in solutions.
Chem Sci
January 2025
School of Chemistry and Chemical Engineering, Shandong University Jinan 250100 PR China
Noncovalent forces have a significant impact on photophysical properties, and the flexible employment of weak forces facilitates the design of novel luminescent materials with a variety of applications. The arene-perfluoroarene (AP) force, as one type of π-hole/π interaction, shows unique directionality, involving an electron-deficient π-hole interacting with a π-electron-rich region, facilitating precise orientation and stabilization in supramolecular structures. Here we present an amination engineering protocol to build a perfluoroarene library based on an octafluoronaphthalene skeleton with various steric and electronic properties.
View Article and Find Full Text PDFSignificant Efficiency Enhancements in Non-Y Series Acceptors by the Addition of Outer Side Chains.
Adv Sci (Weinh)
January 2025
Department of Chemistry and Centre for Processable Electronics, Imperial College London, London, W12 0BZ, UK.
Most current highly efficient organic solar cells utilize small molecules like Y6 and its derivatives as electron acceptors in the photoactive layer. In this work, a small molecule acceptor, SC8-IT4F, is developed through outer side chain engineering on the terminal thiophene of a conjugated 6,12-dihydro-dithienoindeno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (IDTT) central core. Compared to the reference molecule C8-IT4F, which lacks outer side chains, SC8-IT4F displays notable differences in molecule geometry (as shown by simulations), thermal behavior, single-crystal packing, and film morphology.
View Article and Find Full Text PDFSteric and Electronic Effects of Zirconocenealkyl-Borate Ion Pairs on Catalyst Activation: A Theoretical Study.
ACS Omega
January 2025
Unit of Excellence in Computational Molecular Science and Catalysis, and Division of Chemistry, School of Science, University of Phayao, Phayao 56000, Thailand.
The effectiveness of metallocene catalysts in the cationic ring-opening polymerization (cationic ROP) of ε-caprolactone (CL) is influenced by the choice of metallocene/borate systems, particularly their bulkiness. Recent research examines this effect on the initiation and propagation stages of cationic ROP. We conducted a density functional theory study on the precatalyst activation of cationic CL ROP by zirconocene/borate catalysts, where four models of zirconocene precatalysts (CpZrMe (), (MeCp)CpZrMe (), (MeCp)ZrMe (), and IndZrMe ()) were combined with boron cocatalysts B(CF) and [X][B(CF) ] (X = PhC or PhMeNH).
View Article and Find Full Text PDFAn Open-Shell Fe Nitrido.
J Am Chem Soc
January 2025
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
We report the photogeneration and characterization of an open-shell, terminal iron nitrido (L)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe-N distance in the solid-state, zero-field Fe Mössbauer spectrum, and computational analysis are consistent with a triplet electronic ground state of the iron nitrido. Notably, the attenuation of Fe-N multiple bond character through occupying π* enables (i) primary C(sp)-H amination, (ii) H cleavage, (iii) aromatic C-C cleavage, and (iv) photocatalytic -atom transfer reactivity.
View Article and Find Full Text PDFHigh-throughput screening of acetals/ketals in edible essences via GC-Orbitrap-MS and their formation rates at room temperature.
Food Chem
January 2025
Zhengzhou Tobacco Research Institute of CNTC, Zhengzhou, Henan 450001, China.
Flavors contain active aldehydes and ketones that react with glycerol and propylene glycol to form acetals and ketals. The identification of acetals and ketals is challenging due to the incomplete information in mass spectral libraries. This study examines the reaction kinetics of 36 aldehydes and ketones with propylene glycol and glycerol, and establishes a high sensitivity and throughput screening method for 185 acetals and ketals using GC-Orbitrap-MS.
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