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Updated: Aug 16, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Crystal Structures of Ce(IV) Nitrates with Bis(2-pyrrolidone) Linker Molecules Deposited from Aqueous Solutions with
Ryoma Ono1, Hiroyuki Kazama1, Juliane März2
1Laboratory for Zero-Carbon Energy, Institute of Innovative Research, Tokyo Institute of Technology, 2-12-1 N1-32, O-okayama, Meguro-ku, Tokyo152-8550, Japan.
Abstract:
We investigated the molecular and crystal structures of Ce(IV) compounds deposited under different [HNO3] with bis(2-pyrrolidone) linker molecules having a trans-1,4-cyclohexyl bridging moiety (L). As a result, we found that, after loading L, Ce(IV) in HNO3(aq) exclusively provides one of different crystalline phases, (HL)2[Ce(NO3)6] or [Ce2(μ-O)-(NO3)6(L)2] 2D MOF, depending on [HNO3]. The former has been obtained at [HNO3] = 4.70-9.00 M and is isomorphous with the analogous (HL)2[An(NO3)6] we reported previously. In contrast, the deposition of the latter phase at the lower [HNO3] conditions (1.00-4.30 M) demonstrates that hydrolysis and oxolation of Ce4+ proceed even below pH 0 to provide a [Ce-O-Ce]6+ unit included in this compound. These different Ce(IV) phases are exchangeable with each other under soaking in HNO3(aq), implying that chemical equilibria of dissolution/deposition of these crystalline phases and hydrolysis and oxolation of Ce4+ and its complexation with NO3- occur in parallel. Indeed, such coordination chemistry of Ce(IV) in HNO3(aq) was well corroborated by 17O NMR, Raman, and IR spectroscopy.
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