The restriction of intramolecular rotation has been extensively exploited to trigger the property enhancement of nanocluster-based materials. However, such a restriction is induced mainly by intermolecular aggregation. The direct restriction of intramolecular rotation of metal nanoclusters, which could boost their properties at the single molecular level, remains rarely explored. Here, ligand engineering was applied to activate intramolecular interactions at the interface between peripheral ligands and metallic kernels of metal nanoclusters. For the newly reported AuAg(SPhCl)(DPPM) nanocluster, the molecule-level interactions between the Cl terminals on thiol ligands and the Ag atoms on the cluster kernel remarkably restricted the intramolecular rotation, endowing this robust nanocluster with superior thermal stability, emission intensity, and non-linear optical properties over its cluster analogue. This work presents a novel case of the restriction of intramolecular rotation (, intramolecular interaction-induced property enhancement) for functionalizing metal clusters at the single molecular level.
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http://dx.doi.org/10.1039/d3sc01698f | DOI Listing |
Chem Asian J
December 2024
Birla Institute of Technology & Science Pilani - Hyderabad Campus, Chemistry department, Shameerpet, 500078, Hyderabad, INDIA.
The incorporation of photoactive organic dyes into layered inorganic materials enhances their optical and chemical properties, making them ideal for sensing applications. In this study, Bisindolyl methane (BIM)-based neutral probes were integrated with bentonite clay to explore their sensing capabilities. Probe 1 (unoxidized BIM) and Probe 2 (oxidized BIM) generally exhibited quenched luminescence in solution due to intramolecular rotations.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias─I.U. CINQUIMA, Paseo de Belén, 7, 47011 Valladolid, Spain.
The conformational space of 3-chloropropionic acid has been studied under the isolated conditions of a supersonic expansion using Stark-modulated free-jet absorption millimeter-wave and centimeter-wave chirped-pulse Fourier transform microwave spectroscopy techniques. The rotational spectra originating from the three most stable conformers including Cl and Cl isotopologues were observed in both experiments using helium expansion while a partial conformational relaxation involving skeletal rearrangements takes place in an argon expansion. The rotational parameters, geometries, and energy order were determined from the experiment, allowing a comparison with quantum chemical predictions.
View Article and Find Full Text PDFJ Chem Theory Comput
December 2024
Theoretical Chemistry Division, Institute of General, Inorganic and Theoretical Chemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
This work introduces a dedicated thermostatization strategy for molecular dynamics simulations of gaseous systems. The proposed thermostat is based on the stochastic canonical velocity rescaling approach by Bussi and co-workers and is capable of ensuring an equal distribution of the kinetic energy among the translational, rotational, and vibrational degrees of freedom. The outlined framework ensures the correct treatment of the kinetic energy in gaseous systems, which is typically not the case in standard approaches due to the limited number of collisions between particles associated with a large free mean path.
View Article and Find Full Text PDFChem Soc Rev
December 2024
Hefei National Research Center for Physical Sciences at the Microscale, Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, and National Synchrotron Radiation Laboratory, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, Anhui 230026, China.
J Agric Food Chem
December 2024
CAS Key Laboratory of Environmental and Applied Microbiology, Environmental Microbiology Key Laboratory of Sichuan Province, Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, China.
BcABA3 is an unusual sesquiterpene synthase that lacks the conserved DDxxD and DTE/NSE motifs. Despite this, it can catalyze the conversion of farnesyl diphosphate to 2Z,4E-α-ionylideneethane. We used structure prediction, multiscale simulations, and site-directed mutagenesis experiments to investigate BcABA3 and its catalytic mechanism.
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