We have studied the halogen-bonding interactions of a pyridine-functionalized fluoroborate dye with perfluorohaloarenes (CF, CFCl, CFBr, and CFI) in the two-component-only liquid phase using fluorescence spectroscopy. Based on the results of spectroscopic measurements and electronic-structure calculations, we have confirmed the stability only for the complex between CFI and the emissive dye, and it has been demonstrated that halogen-bonding interactions are accompanied by significant Stokes shifts for the ππ* band. We also provide experimental evidence that for this complex, the emission is quenched due to a simultaneous decrease of radiative and increase of nonradiative decay rate constants upon halogen-bonding interactions.
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http://dx.doi.org/10.1021/acs.joc.2c01660 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Indian Institute of Science Education and Research Pune, Chemistry, Dr. Homi Bhabha Road, 411008, Pune, INDIA.
Two-dimensional (2D) chiral hybrid perovskites A2PbI4 (A: chiral organic ion) enable chirality controlled optoelectronic and spin-based properties. A+ organic sublattice induces chirality into the semiconducting [PbI4]2- inorganic sublattice through non-covalent interactions at organic-inorganic interface. Often, the A+ cations in the lattice have different orientations, leading to asymmetry in the non-covalent interactions.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Oklahoma State University, 107 Physical Sciences, Stillwater, Oklahoma 74078, United States.
While charge-transfer complexes involving halogen-bonding interactions have emerged as an alternative strategy for the photogeneration of carbon radicals, examples using (fluoro)alkyl bromides are limited. This report describes a dual catalytic approach for radical generation from α-bromodifluoroesters and amides under visible-light irradiation. Mechanistic studies suggest that the reaction proceeds through bromide displacement using a catalytic iodide salt, generating a C-I bond that can be engaged by our halogen-bonding photocatalysis platform.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
School of Applied and Interdisciplinary Sciences, Indian Association for the Cultivation of Science (IACS), 2A and 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
This study explores peptide-mediated chiral induction and circularly polarized luminescence (CPL) in achiral BODIPY dyes, leading to a high value of up to -1.2 × 10 through orthogonal halogen bonding and hydrogen bonding. It unravels the impact of these combined directional interactions on the formation of heterostructures and their thermal stability.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia.
Halogen-bonding (XB) interactions have been extensively studied in the preparation of crystalline frameworks, yet porous 3D framework materials built on XBs remain elusive. The donor-acceptor interactions are strengthened by use of anionic XB acceptors; however, the requisite charge-balancing cations typically disrupt the framework and occupy potential void space. In this work, we prepare a tetratopic XB donor bearing a crown ether moiety for sodium cation sequestration.
View Article and Find Full Text PDFInt J Mol Sci
November 2024
Research Institute of Chemistry, Peoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia.
Herein, we describe a novel coupling between ambiphilic 2-pyridylselenyl reagents and nitriles featuring an active α-methylene group. Depending on the solvent employed, this reaction can yield two distinct types of cationic pyridinium-fused selenium-containing heterocycles, 1,3-selenazolium or 1,2,4-selenadiazolium salts, in high yields. This is in contrast to what we observed before for other nitriles.
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