The absorption and emission spectra of two coumarins namely 7, 8 benzo-4-azidomethyl coumarin (C(1)) and 6-methoxy-4-azidomethyl coumarin (C(2)) have been recorded at room temperature in solvents of different polarities. The ground state dipole moments (μ(g)) of two coumarins were determined experimentally by Guggenheim method. The exited state (μ(e)) dipole moments were estimated from Lippert's, Bakhshievs and Chamma-Viallet's equations by using the variation of Stoke's shift with the solvent dielectric constant and refractive index. The ground and excited state dipole moments were calculated by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was observed that dipole moments of excited state were higher than those of the ground state, indicating a substantial redistribution of the π-electron densities in a more polar excited state for two coumarins.
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http://dx.doi.org/10.1007/s10895-011-0939-7 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Guangzhou University, Center for Advanced Analytical Science, c/o School of Chemistry and Chemical Engineering, 230 Wai Huan Xi Road, Guangzhou Higher Education Mega Center, Guangzhou 510006 P, 510006, Guangzhou, CHINA.
The optimization of morphology in all-polymer solar cells (all-PSCs) often relies on the use of solvent additives. However, their tendency to remain trapped in the device due to high boiling points leads to performance degradation over time. In this study, we introduce a novel approach involving the design and synthesis of one dual-asymmetric solid additive featuring mono-brominated-asymmetric dithienothiophene (SL-1).
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan.
We investigated the gas-liquid interface of aqueous solutions containing phenol and related aromatic compounds using extreme ultraviolet laser photoelectron spectroscopy and molecular dynamics simulations. The interfacial densities of protonated and deprotonated forms of phenol, aniline, and 4-nitrophenol were found to be primarily determined by their surface affinities and exhibit similar concentration dependences to their respective bulk densities. Despite the distinct interfacial orientations of their permanent dipole moments, these compounds monotonically decreased the surface potential at higher concentrations.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus, Denmark.
The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic quantities is an attractive approach for deriving electrostatic parameters in force fields. The MBIS-derived atomic charges, however, in general tend to overestimate the molecular dipole and quadrupole moments by ∼10%. We show that it is possible to derive a constrained MBIS model where the atomic charges or a combination of atomic charges and dipoles exactly reproduce the molecular dipole and quadrupole moments for molecules.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Microsoft Research AI for Science, 21 Station Road, Cambridge CB1 2FB, United Kingdom.
Variational ab initio methods in quantum chemistry stand out among other methods in providing direct access to the wave function. This allows, in principle, straightforward extraction of any other observable of interest, besides the energy, but, in practice, this extraction is often technically difficult and computationally impractical. Here, we consider the electron density as a central observable in quantum chemistry and introduce a novel method to obtain accurate densities from real-space many-electron wave functions by representing the density with a neural network that captures known asymptotic properties and is trained from the wave function by score matching and noise-contrastive estimation.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Pharmacy, Yantai University, Yantai 264005, P. R. China.
Compared with the energetically favorable 5- or 6-membered fluoro-functionalized heterocycles, the construction of medium-sized fluoro-heterocycles is relatively under-researched because of their inherently unfavorable enthalpic and entropic nature. Based on rational design and DFT calculations, a novel photocatalytic difluoromethyl radical-initiated intramolecular 7--trig cyclization was realized, thus affording a sustainable route for the synthesis of challenging fluoro-functionalized medium-sized -heterocycles. Depending on atomic dipole moment corrected Hirshfeld population (ADCH) charge calculations, the chemoselective 6--trig radical cyclizations were further replenished.
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