Benzene dimer is a prototype to study intermolecular interactions between aromatic systems. Owing to the weak interactions between the molecules within the dimer, several conformational geometries are nearly isoenergetic and thus coexist even at low temperatures. Furthermore, standard spectroscopies are unable to distinguish between them. In this work, we study the electronic relaxation processes following inner-valence ionization of benzene and the lowest conformers of benzene dimer. We show that the kinetic energy distributions of the secondary electrons emitted via two autoionization mechanisms, namely, the Auger and the intermolecular coulombic decay (ICD) effects, provide a means to probe the conformers of benzene dimer. The proposed spectroscopy opens the way to a better characterization of weakly bound molecular clusters.
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http://dx.doi.org/10.1021/acs.jpca.6b09501 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is typically explained in terms of quadrupole-quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry and Biochemistry, University of California, San Diego La Jolla California 92093 USA
Metal-organic frameworks (MOFs) can be prepared from oligomeric organic ligands to prepare materials referred to as oligoMOFs. Studies of oligoMOFs are relatively limited, with most existing reports focused on fundamental structure-property relationships. In this report, functional groups, such as terminal alkynes and pyridine groups, are installed on the tether between 1,4-benzene dicarboxylic acid (Hbdc) groups of the dimer ligands.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
January 2025
Department of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia.
The asymmetric unit of the title compound, CHN·Br·CFI, contains one 2,2,6,6 tetra-methyl-piperidine-1-ium cation, one 1,2,3,4-tetra-fluoro-5,6-di-iodo-benzene mol-ecule, and one uncoordinated bromide anion. In the crystal, the bromide anions link the 2,2,6,6-tetra-methyl-piperidine mol-ecules by inter-molecular C-H⋯Br and N-H⋯Br hydrogen bonds, leading to dimers, with the coplanar 1,2,3,4-tetra-fluoro-5,6-di-iodo-benzene mol-ecules filling the space between them. There is a π-π interaction between the almost parallel benzene rings [dihedral angle = 10.
View Article and Find Full Text PDFSci Rep
December 2024
Department of Biophysics, Faculty of Environmental Biology, University of Life Sciences in Lublin, Akademicka 13, 20-950, Lublin, Poland.
We present a comprehensive spectroscopic study supported by theoretical quantum chemical calculations conducted on a molecular system (4-(5-methyl-1,3,4-thiadiazol-2-yl)benzene-1,3-diol (C1) and the antibiotic Amphotericin B (AmB)) that exhibits highly synergistic properties. We previously reported the strong synergism of this molecular system and now wish to present related stationary measurements of UV-Vis absorption, fluorescence, and fluorescence anisotropy in a polar, aprotic solvent (DMSO and a PBS buffer), followed by time-resolved fluorescence intensity and anisotropy decay studies using different ratios of the selected 1,3,4-thiadiazole derivative to Amphotericin B. Absorption spectra measured for the system revealed discrepancies in terms of the shapes of absorption bands, particularly in PBS.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa Wako, Saitama 351-0198, Japan.
[Pt(NCN)MeCN] (NCN = 1,3-di(2-pyridyl)benzene, MeCN = acetonitrile) forms oligomers in the ground state due to metallophilic interactions, and a Pt-Pt bond is formed with photoexcitation. Ultrafast excited-state dynamics of the [Pt(NCN)MeCN] dimer in acetonitrile is investigated by femtosecond time-resolved absorption (TA) and picosecond emission spectroscopy. The femtosecond TA signals exhibit 60 cm oscillations arising from the Pt-Pt stretching motion in the S dimer.
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