1,3-Adamantanedicarboxylate and 1,3-Adamantanediacetate as Uranyl Ion Linkers: Effect of Counterions, Solvents and Differences in Flexibility

Pierre Thuéry (1) , Youssef Atoini (2) , Jack Harrowfield (2)

1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
2 ISIS - Institut de Science et d'ingénierie supramoléculaires

Seven homo-or heterometallic uranyl ion complexes with 1,3-adamantanedicarboxylic acid (H$_2$ADC) or 1,3-adamantanediacetic acid (H$_2$ADA) have been synthesized under solvo-hydrothermal conditions in the presence of different counterions and organic cosolvents, and characterized by their crystal structure and uranyl emission spectrum. [PPh$_3$Me][UO$_2$(ADC)(NO$_3$)] (1) crystallizes as a simple monoperiodic chain, but [PPh$_4$]$_2$[(UO$_2$)$_2$(ADC)$_3$]. 2H$_2$O (2) and [PPh$_4$]$_2$[(UO$_2$)$_2$(ADA)$_3$] (3) display trough-like monoperiodic assemblies (assembled in pairs in 3) in the cavity of which the counterions are located. A similar arrangement is found in [Ni(cyclen)(H$_2$O)][(UO$_2$)$_2$(ADC)$_3$].H$_2$O (4). Diaxial bonding of Ni II in [(UO$_2$)$_2$(ADC)$_2$Ni(R,S-Me$_6$cyclam)(HCOO)$_2$].CH$_3$CN (5) and [UO$_2$(ADA)$_2$Ni(R,S-Me$_6$cyclam)] (6) results in bridging monoperiodic uranyl-containing subunits into neutral, diperiodic networks. [UO$_2$(ADA)(DMPU)] (7), containing coordinated N,N′-dimethylpropyleneurea, is also a diperiodic assembly with the common fes topological type. Except complex 6 which is non-luminescent, all complexes give solid-state emission spectra displaying the usual vibronic fine structure, albeit with low photoluminescence quantum yields.

Domains: Material chemistry; Cristallography

Pierre Thuéry, Youssef Atoini, Jack Harrowfield. 1,3-Adamantanedicarboxylate and 1,3-Adamantanediacetate as Uranyl Ion Linkers: Effect of Counterions, Solvents and Differences in Flexibility. European Journal of Inorganic Chemistry, 2019, 2019, pp.4440-4449. ⟨10.1002/ejic.201900957⟩. ⟨cea-02311018⟩