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Synthesis, structure, properties, and cytotoxicity of a (quinoline)RuCp + complex
Metal quinoline complexes were prepared using a quinoline-based proteasome inhibitor (Quin1) and an inactive quinoline ligand (Quin2), and their cytotoxicities are reported towards multiple myeloma-related cell lines.
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- Award ID(s):
- 1953254
- PAR ID:
- 10473745
- Publisher / Repository:
- Royal Chemical Society
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 52
- Issue:
- 3
- ISSN:
- 1477-9226
- Page Range / eLocation ID:
- 721 to 730
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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We report results from experiments with the quinoline-O2 complex, which was photodissociated using light near 312 nm. Photodissociation resulted in formation of the lowest excited state of oxygen, O2 a 1Δg, which we detected using resonance enhanced multiphoton ionization and velocity map ion imaging. The O2+ ion image allowed for a determination of the center-of-mass translational energy distribution, P(ET), following complex dissociation. We also report results of electronic structure calculations for the quinoline singlet ground state and lowest energy triplet state. From the CCSD/aug-cc-pVDZ//(U)MP2/cc-pVDZ calculations, we determined the lowest energy triplet state to have ππ* electronic character and to be 2.69 eV above the ground state. We also used electronic structure calculations to determine the geometry and binding energy for several quinoline-O2 complexes. The calculations indicated that the most strongly bound complex has a well depth of about 0.11 eV and places the O2 moiety above and approximately parallel to the quinoline ring system. By comparing the experimental P(ET) with the energy for the singlet ground state and the lowest energy triplet state, we concluded that the quinoline product was formed in the lowest energy triplet state. Finally, we found the experimental P(ET) to be in agreement with a Prior translational energy distribution, which suggests a statistical dissociation for the complex.more » « less
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The platinum(II) complexes of known quinoline-annulated porphyrins were prepared and spectroscopically characterized. Their optical properties (UV-vis absorption and phosphorescence spectra and phosphorescence lifetimes) were recorded and contrasted against their 2,3-dioxoporphyrin precursor platinum(II) complex. The absorbance and emission spectra (in EtOH glass at 77 K) of the quinoline-annulated porphyrins fall within the NIR optical window of tissue, ranging, depending on the derivative, between [Formula: see text]950 and 1200 nm. The much red-shifted optical spectra, when compared to their non-quinoline-annulated precursors, are attributed to the [Formula: see text]-extension and conformational non-planarity that the annulation causes. The emission yields of the mono-quinoline-annulated derivatives are too low and their lifetimes too short to be practical emitters, but the bis-annulated derivative possesses a practical lifetime and emission yield, suggesting its further exploration, particularly since the methodology toward the solubilization of the quinoline-annulated porphyrins in biological media through derivatization is known.more » « less
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The Ru–H complex (PCy 3 ) 2 (CO)RuHCl (1) was found to be a highly effective catalyst for the three-component deaminative coupling reaction of anilines with aldehydes and allylamines to form 2,3-disubstituted quinoline products. The analogous coupling reaction of anilines with aldehydes and cyclic enamines led to the selective formation of the tricyclic quinoline derivatives. The reaction profile study showed that the imine is initially formed from the dehydrative coupling of aniline and aldehyde, and it undergoes the deaminative coupling and annulation reaction with amine substrate to form the quinoline product. The catalytic coupling method provides a step-efficient synthesis of 2,3-disubstituted quinoline derivatives without employing any reactive reagents or forming wasteful byproducts.more » « less
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Abstract An intramolecular SNAr displacement of oneo‐fluorine atom of ameso‐pentafluorophenyl‐substituted porphyrin metal complex by a neighboring β‐amino functionality generated the correspondingmeso‐fluorophenyl‐substituted metallo‐quinolino[2,3,4‐at]porphyrins that are not accessible using established quinoline‐annulation methodologies. The Cu(II), Ni(II), and Zn(II) complexes were thus prepared. The parent free base quinolino[2,3,4‐at]porphyrin is accessible only by demetallation of the copper or zinc complexes. A strong through‐space NMR‐spectroscopic coupling between the remainingo‐fluorine atoms on the annulatedmeso‐aryl group and the β‐hydrogen atom on the adjacent pyrrole moiety provide a clear spectroscopic signature for the annulation. Quinoline‐annulation alters the optical properties significantly. On account of the presence of the β‐amino functionality, all quinoline‐annulated porphyrins show strong halochromic responses with Brønsted acids and bases, the prerequisite for their potential use in chemosensing applications.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2dt03484k
