Magnetic anisotropy of endohedral lanthanide ions: paramagnetic NMR study of MSc2N@C80-Ih with M running through the whole 4f row

Zhang, Yang; Krylov, Denis; Rosenkranz, Marco; Schiemenz, Sandra; Popov, Alexey A.

doi:10.1039/c5sc00154d

Cited by 51 publications

(45 citation statements)

References 107 publications

(108 reference statements)

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“…This approach has been shown to be very successful in calculating 1 H Fermi contact shifts of Tb III complexes with macrocyclic ligands 50. A similar approach was recently utilized in the analysis of NMR spectra of a series of endohedral lanthanoid complexes 51…”

Section: Resultsmentioning

confidence: 99%

DNA Intercalating Ru^II Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

Mari

Pierroz

Rubbiani

et al. 2014

Chemistry A European J

181

272

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Six substitutionally inert [Ru(II) (bipy)2 dppz](2+) derivatives (bipy=2,2'-bipyridine, dppz=dipyrido[3,2-a:2',3'-c]phenazine) bearing different functional groups on the dppz ligand [NH2 (1), OMe (2), OAc (3), OH (4), CH2 OH (5), CH2 Cl (6)] were synthesized and studied as potential photosensitizers (PSs) in photodynamic therapy (PDT). As also confirmed by DFT calculations, all complexes showed promising (1) O2 production quantum yields, well comparable with PSs available on the market. They can also efficiently intercalate into the DNA double helix, which is of high interest in view of DNA targeting. The cellular localization and uptake quantification of 1-6 were assessed by confocal microscopy and high-resolution continuum source atomic absorption spectrometry. Compound 1, and especially 2, showed very good uptake in cervical cancer cells (HeLa) with preferential nuclear accumulation. None of the compounds studied was found to be cytotoxic in the dark on both HeLa cells and, interestingly, on noncancerous MRC-5 cells (IC50 >100 μM). However, 1 and 2 showed very promising behavior with an increment of about 150 and 42 times, respectively, in their cytotoxicities upon light illumination at 420 nm in addition to a very good human plasma stability. As anticipated, the preferential nuclear accumulation of 1 and 2 and their very high DNA binding affinity resulted in very efficient DNA photocleavage, suggesting a DNA-based mode of phototoxic action.

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Section: Resultsmentioning

confidence: 99%

DNA Intercalating Ru^II Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

Mari

Pierroz

Rubbiani

et al. 2014

Chemistry A European J

181

272

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“…SOMO and SOMO-1 orbitals have U-U antibonding character whereas SOMO-2 through SOMO-5 have U-U bonding character. [84][85][86] Fig. This bond is clearly U(5f)-based.…”

Section: Figmentioning

confidence: 89%

Unwilling U–U bonding in U₂@C₈₀: cage-driven metal–metal bonds in di-uranium fullerenes

Foroutan‐Nejad

Vı́cha

Marek

et al. 2015

Phys. Chem. Chem. Phys.

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Endohedral actinide fullerenes are rare and a little is known about their molecular properties. Here we characterize the U2@C80 system, which was recently detected experimentally by means of mass spectrometry (Akiyama et al., JACS, 2001, 123, 181). Theoretical calculations predict a stable endohedral system, (7)U2@C80, derived from the C80:7 IPR fullerene cage, with six unpaired electrons. Bonding analysis reveals a double ferromagnetic (one-electron-two-center) U-U bond at an rU-U distance of 3.9 Å. This bonding is realized mainly via U(5f) orbitals. The U-U interaction inside the cage is estimated to be about -18 kcal mol(-1). U-U bonding is further studied along the U2@Cn (n = 60, 70, 80, 84, 90) series and the U-U bonds are also identified in U2@C70 and U2@C84 systems at rU-U∼ 4 Å. It is found that the character of U-U bonding depends on the U-U distance, which is dictated by the cage type. A concept of unwilling metal-metal bonding is suggested: uranium atoms are strongly bound to the cage and carry a positive charge. Pushing the U(5f) electron density into the U-U bonding region reduces electrostatic repulsion between enclosed atoms, thus forcing U-U bonds.

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“…[50] As imilar approachw as recently utilized in the analysis of NMR spectra of as eries of endohedral lanthanoid complexes. [51] Contact shifts that arise due to unpaired f-electrons in lanthanoid complexes can be expressed by Equation (10) (in ppm): [46a, 50]…”

Section: Contributions From the Metal-centered Unpaired Electronsmentioning

confidence: 99%

Ligand π‐Radical Interaction with f‐Shell Unpaired Electrons in Phthalocyaninato–Lanthanoid Single‐Molecule Magnets: A Solution NMR Spectroscopic and DFT Study

Damjanović

Morita

Katoh

et al. 2015

Chemistry A European J

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The phthalocyaninato double-decker complexes [M(obPc)2 ](0) (M= Y(III) , Tb(III) , Dy(III) ; obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), along with their reduced ([M(obPc)2 ](-) [P(Ph)4 ](+) ; M=Tb(III) , Dy(III) ) and oxidized ([M(obPc)2 ](+) [SbCl6 ](-) (M=Y(III) , Tb(III) ) counterparts were studied with (1) H, (13) C and 2D NMR. From the NMR data of the neutral (i.e., with one unpaired electron in the ligands) and anionic Tb(III) complexes, along with the use of dispersion corrected DFT methods, it was possible to separate the metal-centered and ligand-centered contributions to the hyperfine NMR shift. These contributions to the (1) H and (13) C hyperfine NMR shifts were further analyzed in terms of pseudocontact and Fermi contact shifts. Furthermore, from a combination of NMR data and DFT calculations, we have determined the spin multiplicity of the neutral complexes [M(obPc)2 ](0) (M=Tb(III) and Dy(III) ) at room temperature. From the NMR data of the cationic Tb(III) complex, for which actually no experimental structure determination is available, we have analyzed the structural changes induced by oxidation from its neutral/anionic species and shown that the interligand distance decreases upon oxidation. The fast electron exchange process between the neutral and anionic Tb(III) double-decker complexes was also studied.

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Magnetic anisotropy of endohedral lanthanide ions: paramagnetic NMR study of MSc₂N@C₈₀-I_h with M running through the whole 4f row

Abstract: Paramagnetic and variable temperature 13C and 45Sc nuclear magnetic resonance studies are performed for nitride clusterfullerenes MSc2N@C80 with icosahedral I h(7) carbon cage, where M runs through all lanthanides forming nitride clusters.

Cited by 51 publications

References 107 publications

DNA Intercalating Ru^II Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

DNA Intercalating Ru^II Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

Unwilling U–U bonding in U₂@C₈₀: cage-driven metal–metal bonds in di-uranium fullerenes

Ligand π‐Radical Interaction with f‐Shell Unpaired Electrons in Phthalocyaninato–Lanthanoid Single‐Molecule Magnets: A Solution NMR Spectroscopic and DFT Study

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Magnetic anisotropy of endohedral lanthanide ions: paramagnetic NMR study of MSc2N@C80-Ih with M running through the whole 4f row

Abstract: Paramagnetic and variable temperature 13C and 45Sc nuclear magnetic resonance studies are performed for nitride clusterfullerenes MSc2N@C80 with icosahedral I h(7) carbon cage, where M runs through all lanthanides forming nitride clusters.

Cited by 51 publications

References 107 publications

DNA Intercalating RuII Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

DNA Intercalating RuII Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

Unwilling U–U bonding in U2@C80: cage-driven metal–metal bonds in di-uranium fullerenes

Ligand π‐Radical Interaction with f‐Shell Unpaired Electrons in Phthalocyaninato–Lanthanoid Single‐Molecule Magnets: A Solution NMR Spectroscopic and DFT Study

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Magnetic anisotropy of endohedral lanthanide ions: paramagnetic NMR study of MSc₂N@C₈₀-I_h with M running through the whole 4f row

DNA Intercalating Ru^II Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

DNA Intercalating Ru^II Polypyridyl Complexes as Effective Photosensitizers in Photodynamic Therapy

Unwilling U–U bonding in U₂@C₈₀: cage-driven metal–metal bonds in di-uranium fullerenes