Pressure-Induced Spectroscopic Changes in a Californium 1D Material Are Twice as Large as Found in the Holmium Analog

• Published in: Inorganic chemistry Vol. 59; no. 15; pp. 10794 - 10801
• Main Authors: Sperling, Joseph M, Warzecha, Evan, Windorff, Cory J, Klamm, Bonnie E, Gaiser, Alyssa N, Whitefoot, Megan A, White, Frankie D, Poe, Todd N, Albrecht-Schönzart, Thomas E
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.08.2020; American Chemical Society (ACS)
• Subjects: Chemistry
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c01290

In this study, the synthesis, characterization, and pressure response of a 1D californium mellitate (mellitate = 1,2,3,4,5,6-benzenehexacarboxylate) coordination polymer, Cf2(mell)­(H2O)10·4H2O (Cf-1), are reported. The Cf–O lengths within the crystal structure are compared to its gadolinium (Gd-1) and holmium (Ho-1) analogs as well. These data show that the average Cf–O bond distance is slightly longer than the average Gd–O bond, consistent with trends in effective ionic radii. UV–vis-NIR absorption spectra as a function of pressure were collected using diamond-anvil techniques for both Cf-1 and Ho-1. These experiments show that the Cf­(III) f → f transitions have a stronger dependence on pressure than that of the holmium analog. In the former case, the shift is nearly linear with applied pressure and averages 6.6 cm–1/GPa, whereas in the latter, it is <3 cm–1/GPa.