Characterization of the interactions between neptunyl and plutonyl cations and expanded porphyrins

Sessler, Jonathan L.; Gorden, Anne E. V.; Seidel, Daniel; Hannah, Sharon; Lynch, Vincent M.; Gordon, Pamela L.; Donohoe, Robert J.; Tait, C. Drew; Keogh, D. Webster

doi:10.1016/s0020-1693(02)01202-1

Cited by 71 publications

(90 citation statements)

References 51 publications

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“…Cesium chloride (0.29 g, 1.7 mmol) was dissolved in 6 M HCl (10 mL), and this solution was added to a stock solution of 0.43 M NpO 2 2+ in 1 M HCl (1.5 mL, 0.65 mmol) [10]. The vial containing the solution was gently stirred for ∼5 min, then covered loosely with parafilm, and allowed to stand for two weeks at room temperature, yielding dark-green blocks in quantitative yield.…”

Section: Synthesis and Characterization Of Cs 2 Npo 2 CL 4 (1)mentioning

confidence: 99%

Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Wilkerson

Arrington

Berg

et al. 2007

Journal of Alloys and Compounds

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Section: Synthesis and Characterization Of Cs 2 Npo 2 CL 4 (1)mentioning

confidence: 99%

Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Wilkerson

Arrington

Berg

et al. 2007

Journal of Alloys and Compounds

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“…On the other hand, several actinide-containing Schiff base macrocycles have been reported by our group [4,[15][16][17][18]. Among these, perhaps the best studied has been 'alaskaphyrin' (2), a 2,5-diformylpyrrolederived Schiff base system that is characterized by its ease of synthesis and its robustness [15].…”

Section: Discussionmentioning

confidence: 99%

“…reported [17]. For these latter studies, it proved preferable to add the metal salt to the preformed macrocycle due to the handling restrictions associated with the use of radioactive cations.…”

Section: Temperature-dependent Xrd Study Of Liquid Crystalline Alaskamentioning

confidence: 99%

“…In all cases, these additions caused significant spectral changes in the UV-vis region that were fully consistent with actinide cation coordination. In addition, crystals of the uranyl complex suitable for X-ray diffraction analysis were obtained [17]. The resulting structure revealed that the macrocycle is nearly planar and that the uranyl cation is displaced slightly in the direction of the dipyrromethene unit.…”

Section: Uv-vis Spectral Evidence For the Coordination Of F-block Catmentioning

confidence: 99%

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Schiff base oligopyrrolic macrocycles as ligands for lanthanides and actinides

Sessler¹,

Melfi²,

Tomat³

et al. 2006

Journal of Alloys and Compounds

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“…44 The expanded porphyrins have 4 -6 nitrogen-containing rings making very large cavities that can accommodate the actinide ions. The actinyl ions bind to the expanded porphyrins in an inner-sphere manner such that the ring of N atoms takes up the equatorial plane, leaving the oxo ligands above and below the porphyrin ring.…”

Section: Macrocyclic Ligandsmentioning

confidence: 99%

Actinides: Inorganic & Coordination ChemistryBased in part on the article Actinides: Inorganic & Coordination Chemistry by Grigorii L. Soloveichik which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Keogh¹

2005

Encyclopedia of Inorganic Chemistry

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The Inorganic and Coordination Chemistry of the 5f elements (Actinides) is intermediate between that of the transition metals and the 4f elements (Lanthanides). The first four members of the actinide series, Ac, Th, Pa, and U, are all naturally occurring but have unstable nuclei, making them radioactive. The other elements in the actinide series (transuranium elements or transuranics) are also radioactive and have been made by man through a variety of nuclear transformation processes, for example, neutron irradiation, atom bombardment, and radioactive decay. The actinide series may be broken into two separate groups, the light or early actinides (Ac–Am) and the heavy or late actinides (Cm–Lr). The chemical behaviors of these two groups are distinct. The light actinides are capable of being stabilized in a variety of oxidation states, for example, II to VII, and have been found to exhibit a significant degree of covalency in binding ligands. The heavy actinides are more reminiscent of the lanthanides in that the most persistent oxidation state is the trivalent and the bonding predominately occurs through ionic interactions. This difference has led to a substantial number of studies into the role of the 5f orbitals in structure and bonding of the actinides. One of the ions that has received a great deal of attention is the ubiquitous actinyl ion, AnO22+/+. This ion is the stable form for all aqueous complexes of the pentavalent and hexavalent light actinides. The oxo ligands are always found in a trans geometry and are strongly bound (triple bond) through a combination of σ‐ and π‐bonds with the 5f and 6d orbitals of the actinide metal center. While these strong covalent interactions exist with the axial oxo ligands, the bonding within the equatorial plane is primarily based on ionic interactions. The ability of the light actinides to access multiple oxidation states leads to rich and, sometimes, complex electrochemistry. For example, under acidic conditions the reduction potentials for PuO 2 2+ , PuO 2 + , Pu 4+ , and Pu 3+ are all close to 1 V. The physical manifestation of these close reduction potentials is an aqueous solution in which the plutonium can exist in four different oxidation states simultaneously. By careful control of the conditions, oxidation state pure solutions can be obtained for quantitative and qualitative studies. The binding affinities of the actinide ions to ligands follow the general trend An 4+ > An 3+ ∼ AnO 2 2+ ≫ AnO 2 + . Since the actinides are strong acids, the ions preferentially bond strong bases, for example, halides, oxygen donors, and so on. Owing to the greater degree of covalency in actinide complexes compared to the lanthanides, complexes with ligands having nitrogen, phosphorus, sulfur, and selenium donors are also found.

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Characterization of the interactions between neptunyl and plutonyl cations and expanded porphyrins

Cited by 71 publications

References 51 publications

Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Schiff base oligopyrrolic macrocycles as ligands for lanthanides and actinides

Actinides: Inorganic & Coordination ChemistryBased in part on the article Actinides: Inorganic & Coordination Chemistry by Grigorii L. Soloveichik which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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