Samantha K. Cary

Area of research

Materials Chemistry · Inorganic Chemistry

Research interest

Research topics from publications: Emergence of californium as the second transitional element in the actinide series; Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state; A series of dithiocarbamates for americium, curium, and californium; Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes; Electronic Structure and Properties of Berkelium Iodates; Incipient class II mixed valency in a plutonium solid-state compound; Chirality and Polarity in the f‐Block Borates M4[B16O26(OH)4(H2O)3Cl4] (M=Sm, Eu, Gd, Pu, Am, Cm, and Cf); Unfolding the physics of URu2Si2 through silicon to phosphorus substitution; Why Is Uranyl Formohydroxamate Red?; Monomers, Dimers, and Helices: Complexities of Cerium and Plutonium Phenanthrolinecarboxylates. Representative work: A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a Berkelium is positioned at a crucial location in the actinide series between the inherently stable half-filled 5f(7) configuration of curium and the abrupt transition in chemical behavior created by the onset of a metastable divalent state that starts at californium. However, the mere 320-day half-life of berkelium's only available isotope, (249)Bk, has hindered in-depth studies of the element's coordination chemistry. Herein, we report the synthesis and detailed solid-state and solution-phase characterization of a berkelium coordination complex, Bk(III)tris(dipicolinate), as well as a chemically distinct Bk(III) borate material for comparison. We demonstrate that berkelium's complexation is

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