%0 Journal Article
%A Mizuoka, Koichiro
%A Tsushima, Satoru
%A Hasegawa, Miki
%A Hoshi, Toshihiko
%A Ikeda, Yasuhisa
%D 2005
%T Electronic Spectra of Pure Uranyl(V) Complexes: Characteristic
Absorption Bands Due to a UVO2+ Core in Visible and Near-Infrared
Regions1
%U https://acs.figshare.com/articles/journal_contribution/Electronic_Spectra_of_Pure_Uranyl_V_Complexes_Characteristic_Absorption_Bands_Due_to_a_U_sup_V_sup_O_sub_2_sub_sup_sup_Core_in_Visible_and_Near_Infrared_Regions_sup_1_sup_/3269719
%R 10.1021/ic0503838.s001
%2 https://ndownloader.figshare.com/files/5107438
%K 2 DMSO
%K dbm
%K U V O 2
%K NIR
%K CO 3
%K saloph
%K 5 f 1 configuration
%K cm
%K complex
%K nm
%K uranyl
%K absorption bands
%X To clarify the electronic spectral properties of uranyl(V) complexes systematically, we measured absorption spectra
of three types of pure uranyl(V) complexes: [UVO2(dbm)2DMSO]-, [UVO2(saloph)DMSO]-, and [UVO2(CO3)3]5-
(dbm = dibenzoylmethanate, saloph = N,N‘-disalicylidene-o-phenylenediaminate, DMSO = dimethyl sulfoxide).
As a result, it was found that these uranyl(V) complexes have characteristic absorption bands in the visible−near-infrared (NIR) region, i.e., at around 640, 740, 860, 1470, and 1890 nm (molar absorptivity, ε = 150−900 M-1·cm-1)
for [UVO2(dbm)2DMSO]-, 650, 750, 900, 1400, and 1875 nm (ε = 100−300 M-1·cm-1) for [UVO2(saloph)DMSO]-,
and 760, 990, 1140, 1600, and 1800 nm (ε = 0.2−3.6 M-1·cm-1) for [UVO2(CO3)3]5-. These characteristic absorption
bands of the uranyl(V) complexes are attributable to the electronic transitions in the UVO2+ core because the
spectral features are similar to each other despite the differences in the ligands coordinated to the equatorial plane
of the UVO2+ moiety. On the other hand, the ε values of [UVO2(CO3)3]5- are quite smaller than those of
[UVO2(dbm)2DMSO]- and [UVO2(saloph)DMSO]-. Such differences can be explained by the different coordination
geometries around the center uranium in these uranyl(V) complexes. Consequently, the absorption bands of the
uranyl(V) complexes in visible−NIR region were assigned to f−f transitions in the 5f1 configuration.
%I ACS Publications