Tetraarylporphyrins substituted with nitro groups at beta-pyrrolic positions are potential candidates for electron-accepting pigments in model systems for photosynthesis. The photophysics of 2-nitro-5,10,15,20-tetra-p-tolylporphyrin and its zinc analog have been studied in order to evaluate this potential. The ground state absorption spectrum, the triplet-triplet absorption spectrum, the fluorescence emission spectrum, and associated photophysical parameters have been determined. The molecules have short singlet lifetimes and anomalous temperature- and solvent-dependent emission spectra which are consistent with the formation of an intramolecular charge transfer state of the type P+.-NO2-. in which the nitro group is twisted about its bond to the porphyrin, relative to the ground state conformation.
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http://dx.doi.org/10.1111/j.1751-1097.1990.tb01733.x | DOI Listing |
Acad Emerg Med
January 2025
Department of Emergency Medicine, University of Rochester, Rochester, New York, USA.
Background: Cervical cancer (CC) is preventable. CC screening decreases CC mortality. Emergency department (ED) patients are at disproportionately high risk for nonadherence with CC screening recommendations.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
College of Science and Engineering, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia.
We report the results of a study of the interaction between torsion and the low frequency out-of-plane silyl wag vibration in the ground, S, and excited, S, electronic states of phenylsilane. These studies follow the observation of interactions between methyl torsion and the out-of-plane methyl wagging vibration in toluene, several fluoro-substituted toluenes and -methylpyrrole. The interaction leads to various spectroscopic constants becoming divorced from their usual physical meaning.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637, United States.
Hybrid quantum-classical computing algorithms offer significant potential for accelerating the calculation of the electronic structure of strongly correlated molecules. In this work, we present the first quantum simulation of conical intersections (CIs) in a biomolecule, cytosine, using a superconducting quantum computer. We apply the contracted quantum eigensolver (CQE)─with comparisons to conventional variational quantum deflation (VQD)─to compute the near-degenerate ground and excited states associated with the conical intersection, a key feature governing the photostability of DNA and RNA.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Laboratorium für Organische Chemie, Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich 8093, Switzerland.
We report spectroscopic and spectrometric experiments that probe the London dispersion interaction between -butyl substituents in three series of covalently linked, protonated -pyridines in the gas phase. Molecular ions in the three test series, along with several reference molecules for control, were electrosprayed from solution into the gas phase and then probed by infrared multiphoton dissociation spectroscopy and trapped ion mobility spectrometry. The observed N-H stretching frequencies provided an experimental readout diagnostic of the ground-state geometry of each ion, which could be furthermore compared to a second, independent structural readout via the collision cross section.
View Article and Find Full Text PDFDalton Trans
January 2025
Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster, Germany.
The cadmium-rich intermetallic compounds RhCd ( = Ca, Sr, Y, La-Nd, Sm-Lu) were synthesized from the elements in sealed tantalum tubes. The elements were reacted in an induction furnace and the samples were post-annealed to increase phase purity and crystallinity. The RhCd phases crystallize with the cubic CeCrAl type structure, space group 3̄.
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